CN117865392A - Treatment method of drilling fluid waste liquid - Google Patents
Treatment method of drilling fluid waste liquid Download PDFInfo
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- CN117865392A CN117865392A CN202410043528.0A CN202410043528A CN117865392A CN 117865392 A CN117865392 A CN 117865392A CN 202410043528 A CN202410043528 A CN 202410043528A CN 117865392 A CN117865392 A CN 117865392A
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- 239000007788 liquid Substances 0.000 title claims abstract description 81
- 238000005553 drilling Methods 0.000 title claims abstract description 69
- 239000002699 waste material Substances 0.000 title claims abstract description 67
- 239000012530 fluid Substances 0.000 title claims abstract description 60
- 238000000034 method Methods 0.000 title claims abstract description 27
- 238000005189 flocculation Methods 0.000 claims abstract description 41
- 230000016615 flocculation Effects 0.000 claims abstract description 41
- 125000002091 cationic group Chemical group 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000008394 flocculating agent Substances 0.000 claims abstract description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 17
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- 230000009286 beneficial effect Effects 0.000 description 8
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- 238000003912 environmental pollution Methods 0.000 description 5
- 239000000178 monomer Substances 0.000 description 5
- 238000003860 storage Methods 0.000 description 5
- 229920002472 Starch Polymers 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- 239000004721 Polyphenylene oxide Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
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- 229910001385 heavy metal Inorganic materials 0.000 description 2
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- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
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- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
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Landscapes
- Separation Of Suspended Particles By Flocculating Agents (AREA)
Abstract
The invention relates to a method for treating drilling fluid waste liquid, which specifically comprises the following steps: adding a flocculating agent into the waste drilling fluid, and after the first solid-liquid separation, sequentially performing electric flocculation treatment, air floatation treatment and second solid-liquid separation treatment on the separated fluid to obtain reinjection water; the flocculant is a cationic flocculant. The treatment method of the drilling fluid waste liquid has simple process and can be used in the presentThe method is carried out on production equipment, has good adaptability to field application, treats the drilling fluid waste liquid, contains metal elements and organic matters, and produces COD Cr The content is obviously reduced, and the waste water after the treatment of the drilling waste liquid can be recycled.
Description
Technical Field
The invention relates to a method for treating drilling fluid waste liquid, and belongs to the field of drilling fluid of oil and gas fields in petroleum industry.
Background
With the rapid development of petroleum industry, the types of drilling fluids are continuously increased, and additives are increasingly increased, so that the composition of the drilling fluids is extremely complex, and some components have toxic effects on human bodies and the environment. It is counted that by 2002, 18 kinds of thousands of raw materials and additives are added to national drilling fluid chemicals, and 10 kinds of cement additives are added to the drilling fluid chemicals. Along with the increasing of the consumption of the drilling fluid, the waste drilling fluid is also increased. A1500 m oil well is drilled to generate 300t rock fragments, 2t oil sludge is formed by crude oil falling to the ground, the occupied area of drilling fluid directly formed by the oil well can reach 4 mu, and if the drilling fluid is not treated in time, 10 mu of land on the well edge can be polluted by wind blowing and rain. Therefore, the generated waste drilling fluid and drilling wastewater are not treated or are not properly treated, and the natural environment is possibly seriously polluted, and the generated pollution accidents can further influence the relationship of workers and farmers. It is counted that a common oil-gas well with a diameter of 3000m to 4000m is drilled, and the abandoned drilling fluid after completion is close to 300m 3 . Because the drilling waste liquid has high chromaticity and high solid phase content (21-27 percent), COD cr High content (2649-71940 mg/L), good colloid stability, high oil content of partial wells, difficult direct dehydration and excellent water retention, can not be dried up after being placed in a large soil pool for several years, can not be covered with soil to return to the field, can be piled up on site or discharged at will, has very serious pollution hidden trouble and forms larger environmental pollution.
Application publication number CN105084614A Chinese patent document discloses a drilling fluid waste liquid treatment method, which specifically comprises the following steps: adding a calcium chloride destabilizing system into the drilling fluid waste liquid, after solid-liquid separation, adding a chemical flocculant into the separation liquid to obtain a mixture, mixing the mixture with micro-nano dissolved air water, performing air floatation, and performing electric flocculation treatment on the obtained air floatation water. The method can effectively reduce the contents of metal elements and organic matters in the waste drilling fluid, and the COD of the effluent is obtained Cr Less than 150mg/L.
Disclosure of Invention
The invention aims to provide a treatment method of drilling fluid waste liquid, which realizes the aim of reducing the influence of the drilling fluid waste liquid on the environment, remarkably reduces suspended matters, oil content and the like after the drilling fluid waste liquid is treated, can be repeatedly and comprehensively utilized, and ensures that waste solids meet the aim of environmental protection standards.
In order to achieve the above purpose, the technical scheme of the treatment method of the drilling fluid waste liquid in the invention is as follows:
a treatment method of waste drilling fluid liquid comprises the steps of adding flocculant into waste drilling fluid, performing first solid-liquid separation, and sequentially performing electric flocculation treatment, air floatation treatment and second solid-liquid separation on separated liquid to obtain reinjection water; the flocculant is a cationic flocculant.
The beneficial effects of the technical scheme are that: firstly, a cationic flocculant is selected to treat drilling fluid waste liquid, and after the first solid-liquid separation, the removal rate of COD, turbidity and suspended matters can be up to more than 90%; the separated liquid is treated by electric flocculation to adsorb and precipitate particles in the separated liquid, so that the COD and heavy metal content are effectively reduced; and the electric flocculation treatment liquid is subjected to air floatation treatment to realize oil-water separation, so that COD content and residues in water are further reduced.
As a further improvement, the addition amount of the cationic flocculant is 5-10g/L.
The beneficial effects of the technical scheme are that: the cationic flocculant has the advantages of quick flocculation effect and low biotoxicity, can realize removal rate of COD, turbidity and suspended matters reaching more than 90% at lower use amount, and greatly reduces the risk of environmental pollution and the treatment cost of drilling fluid waste liquid.
As a further improvement, COD is less than or equal to 300mg/L after the electric flocculation treatment, and polyaluminium chloride is added during the air floatation treatment.
The beneficial effects of the technical scheme are that: when COD is less than or equal to 300mg/L after the electric flocculation treatment of the drilling fluid waste liquid, polyaluminium chloride is added during the subsequent air floatation treatment, so that the COD in the drilling fluid waste liquid can be further reduced.
As a further improvement, the addition amount of the polyaluminum chloride is 1-5 g/L.
The beneficial effects of the technical scheme are that: the addition of the polyaluminium chloride with the addition amount and the air floatation treatment can further reduce COD in the drilling fluid waste liquid. And a small amount of polyaluminium chloride is added, so that a good effect can be achieved, and the risk of environmental pollution is reduced.
As a further improvement, COD after the electric flocculation treatment is more than 300mg/L, and polyaluminium chloride and polyacrylamide are added during the air floatation treatment.
The beneficial effects of the technical scheme are that: when COD is more than 300mg/L after the electric flocculation treatment of the drilling fluid waste liquid, polyaluminium chloride and polyacrylamide are added during the subsequent air floatation treatment, and the polyacrylamide is used as a coagulant aid, so that the COD in the drilling fluid waste liquid can be further reduced by matching with the polyaluminium chloride. And the polyacrylamide and the polyaluminium chloride are common treating agents in wastewater treatment, and have wide sources and low cost.
As a further improvement, the addition amount of the polyaluminum chloride is 3-4.5 g/L, and the addition amount of the polyacrylamide is 4-6 mgL.
The beneficial effects of the technical scheme are that: the polyaluminium chloride and the polyacrylamide are matched with air floatation treatment, so that the addition amount of the two substances can be reduced, and the risk of environmental pollution is reduced.
As a further improvement, the solids after the first solid-liquid separation are used for brickmaking and/or well site paving.
The beneficial effects of the technical scheme are that: can effectively utilize solid matters in the waste drilling fluid and further lighten environmental pollution.
Compared with the prior art, the invention has the beneficial effects that:
(1) The waste water after the treatment of the drilling waste liquid can be recycled, and the treated waste liquid can be reinjected after passing through the joint station;
(2) After the waste drilling fluid liquid is treated, the waste solids meet the environmental protection standard, and can be used for making bricks, producing cement and paving well sites, so that the influence of the waste drilling fluid liquid on the environment is reduced;
(3) Land and treatment cost are saved, landfill is not needed or reduced after the waste slurry is treated, the land is saved, and excavation and seepage prevention cost of a landfill pool are saved;
(4) The treatment method of the drilling fluid waste liquid has simple preparation process, can be carried out on the existing production equipment, and has good adaptability to field application.
Drawings
FIG. 1 is a graph showing the chemical coagulation effect (COD content is reduced) of the gel-like drilling fluid in example 2 of the present invention;
FIG. 2 is a flow chart of a method for treating drilling fluid waste liquid in example 3 of the present invention.
Detailed Description
In the invention, the cationic flocculant is selected from cationic flocculants produced in cooperation with Dalian petrochemical institute.
The cationic flocculant comprises a starch structural unit, a zwitterionic monomer structural unit, a polyether structural unit and a cross-linking agent structural unit; the structural formula of the flocculant is as follows in formula (1):
wherein: a represents a zwitterionic monomer structural unit, the structural formula of which is any one of the formulas (2-1), (2-2), (2-3) and (2-4);
wherein m' is 3 or 4;
wherein x: y= (1 to 4): 1, x+y=400 to 1200; n is 2-10; r is H or methyl; m is 1-3; m is a trivalent or higher metal ion.
The preparation process of the cationic flocculant comprises the following steps:
mixing the amphoteric ion graft copolymerization modified starch, polyether and water, dripping a crosslinking agent for crosslinking reaction after uniformly mixing, and carrying out association reaction on the obtained crosslinking substance and inorganic salt solution to obtain the cationic flocculant. The amphoteric ion graft copolymerization modified starch is one or more of N-methyl diallyl propane sulfonate graft copolymerization modified starch, N-dimethyl allyl amine propane sulfonate graft copolymerization modified starch, 4-vinyl pyridine propane sulfonate graft copolymerization modified starch, N-methyl diallyl butane sulfonate graft copolymerization modified starch and methacryloxyethyl-N, N-dimethyl propane sulfonate graft copolymerization modified starch. The amphoteric ion graft copolymerization modified starch is prepared by the following method: (1) Mixing starch with water, and treating under the protection of nitrogen or inert gas to obtain gelatinized starch; (2) Mixing a zwitterionic monomer with water, and then adjusting the pH value of the solution to 8-9 to obtain a zwitterionic monomer aqueous solution; (3) And (3) adding an initiator into the gelatinized starch obtained in the step (1) for reaction, then adding the zwitterionic monomer aqueous solution obtained in the step (2), and further reacting to obtain the zwitterionic graft copolymerization modified starch.
The specific preparation method is shown in Chinese patent application No. CN 113121002B.
The device used in the treatment method of the drilling fluid waste liquid comprises: temporary storage tank, mixing tank, solid-liquid separation device, electric flocculation device, air supporting device and filter equipment. The temporary storage pool is used for storing the collected drilling fluid waste liquid and is communicated with the mixing tank; the mixing tank is used for carrying out flocculation reaction of drilling fluid waste liquid and is connected with the solid-liquid separation device; the solid-liquid separation device is a plate-and-frame filter press or a centrifuge, and is connected with the electric flocculation device through filter pressing or centrifugation to separate solid and liquid phases; the electric flocculation device generates hydroxide with flocculation effect under the action of an external electric field, and the hydroxide is adsorbed and precipitated to remove particles, so that the COD and heavy metal content is reduced, and the electric flocculation device is connected with the air floatation device; the air floatation device is formed by adding air floatation water generated by the micro-nano bubble generating device into the wastewater according to a certain proportion, and the air floatation device is connected with the filtering device by utilizing the large surface area of the micro-nano bubbles and the upward floating of the surfaces of residues and oil drops adsorbed in the wastewater so as to achieve solid-liquid separation and further reduce COD.
The present invention will be further described with reference to the following specific embodiments, and it should be noted that, on the premise of no conflict, new embodiments may be formed by any combination of the embodiments or technical features described below. The equipment and materials used, etc., are commercially available or are conventional in the art. The methods in the following examples are conventional in the art unless otherwise specified.
Example 1 comparison of flocculation effects of calcium chloride and cationic flocculant
Selecting supernatant of B81-1 well drilling waste liquid (namely supernatant of B81-1 well drilling waste liquid after natural sedimentation), wherein COD is 71940mg/L, and adding CaCl with different concentrations into the supernatant respectively 2 And a cationic flocculant, and the flocculation effect of the two substances is compared, and the results are shown in Table 1. As can be seen from Table 1, compared with CaCl 2 The same amount of cationic flocculant is added, so that the flocculation effect on the supernatant fluid of the B81-1 well drilling waste liquid is better.
TABLE 1CaCl 2 Flocculation effect comparison of cationic flocculant
Example 2 evaluation of flocculant in air flotation stage
Aiming at the characteristics of drilling waste liquid, the chemical flocculant used in the air floatation stage is unfoldedFlocculation effect evaluation experiment, PAC (polyaluminum chloride), PFS (polymeric ferric sulfate) and CaCl are selected 2 And (3) performing flocculation effect evaluation experiments on the three flocculating agents. The drilling waste liquid adopts an L848 well polymer system, the COD of the waste liquid is 2480mg/L, and the experimental results are shown in Table 2.
Table 2PFS, PAC, caCl 2 Evaluation of flocculation Effect on L848 Polymer System
According to the experimental result, caCl is added under the same addition amount 2 The flocculation effect is worst, and PAC and PFS can achieve better flocculation effect under the condition of less addition.
And further carrying out flocculation effect evaluation on the PAC and PFS two flocculants according to the previous experimental results, and carrying out flocculation effect evaluation experiments under the condition of equal addition. The drilling waste liquid uses D12 well polymer system soil Chi Feiye, the COD of the waste liquid is 203.2mg/L, and the experimental results are shown in Table 3.
TABLE 3 comparison of flocculation Effect of PAC, PFS on D12 well Polymer System Large soil pond waste liquid
According to the experimental results, PAC is equivalent to PFS in flocculation effect, but after PFS flocculation, the water quality turns yellow, so PAC is selected as the main flocculant.
In order to further improve the flocculation effect, CPAM (cationic polyacrylamide) and PAM (polyacrylamide) are selected as coagulant aids to carry out flocculation evaluation experiments, D18 well soil pond wastewater is used as drilling waste liquid, COD (chemical oxygen demand) of the waste liquid is 560mg/L, and the results are shown in tables 4-5. According to experimental results, the PAM has better coagulation aiding effect than CPAM.
TABLE 4 test results of CPAM and PAC, PFS compounding
TABLE 5PAM and PAC compounding experimental results
The concentration of PAC is 3.5g/L, and when the concentration of PAM is 6mg/L, the COD of the waste water of the large soil pond of the D18 well is reduced from 560mg/L to 93.31mg/L, so that the COD in the waste water is further reduced.
After gel breaking solid-liquid separation is carried out on the waste liquid (gel jelly) of the B160-1 well, a flocculating agent PAC (3.5 g/L) -coagulant aid PAM (6 mg/L) is sequentially added for treatment, and the COD value is finally reduced to 166mg/L, as shown in figure 1, further illustrating that the compound flocculation effect is better than that of a single agent.
Example 3 treatment method of drilling fluid waste liquid
The flow of the treatment method of the drilling fluid waste liquid in this embodiment is shown in fig. 2, the treatment object is water-based drilling fluid (COD is 1000-11000 mg/L), and the specific implementation operation is as follows:
(1) The waste drilling fluid is transported and stored in a mud temporary storage pool from a drilling well site, is introduced into a mixing tank, is added with a cationic flocculant, is stirred in the mixing tank, and has the addition amount of 10g/L. The flocculated mixture enters a plate-and-frame filter press and is pressurized to 0.2-0.4 MPa, a channel which is formed by pressing small holes is formed in the same part of the middle of the upper ends of a plate and a frame and enters a pressure filtration chamber, grooves are engraved on the surface of a filter plate, a pore canal for discharging filtrate is drilled at the lower end of the filter plate, and the filtrate is discharged out of a filter machine through filter cloth and along the grooves and the pore canal under pressure, so that the mixture is dehydrated, and solid matter mud cakes and waste liquid are obtained; the solid mud cake is transported to a mud shed and then transported out for well site paving and/or brickmaking.
(2) The waste liquid filtered by the plate-and-frame filter press is subjected to electric flocculation treatment, aluminum is used as a polar plate in electric flocculation, and the area of the polar plate required for treating the liquid in unit volume is 80cm 2 The distance between the polar plates is 4.0cm, and the current density is 15mA/cm 2 The electric flocculation treatment time is 30min, and after scum is scraped, electric flocculation effluent is obtained.
(3) The electric flocculation effluent is subjected to air floatation treatment continuously, and the volume ratio of the micro-nano dissolved air water to the mixture is 1:20, mixing dissolved air flotation water with the dissolved air pressure of 0.2MPa and the circulation time of 10min with the electric flocculation effluent water obtained in the step (2), and adding polyacrylamide and polyaluminium chloride with the addition amounts of 6mg/L and 3.5g/L respectively. The air-float effluent enters a filtering tank for filtering, is stored in a buffer tank, is treated by a double-sub flow (Henan oilfield double-river combination station: oilfield water injection flow and process, oil and gas gathering and transportation, sewage treatment and drainage) through a drainage pipeline, and is reinjected into a stratum.
At different time points, liquid is taken at the outlet of the temporary storage tank and the outlet of the filtering device respectively, and the liquid characteristics are analyzed, and the results are shown in Table 6.
TABLE 6 results of liquid Property analysis
| Temporary storage Chi Yeti | Outlet liquid of filter | GB8978 standard limit | |
| COD(mg/L) | 1000～11000 | 32.0-57.0 | <150mg/L |
| Oil (mg/L) | 5000～25000 | 0.88-5.30 | <10mg/L |
| PH value | 7～10 | 7～8 | 7～8 |
According to the experimental result, the sewage treated by the environment-friendly drilling fluid waste liquid treatment device reaches the reinjection standard, so that the pollution of the drilling fluid waste liquid to the environment can be effectively reduced.
The above description is only a preferred embodiment of the present invention, and the patent protection scope of the present invention is defined by the claims, and all equivalent structural changes made by the specification and the drawings of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A method for treating drilling fluid waste liquid is characterized by comprising the following steps: adding a flocculating agent into the waste drilling fluid, and after the first solid-liquid separation, sequentially performing electric flocculation treatment, air floatation treatment and second solid-liquid separation treatment on the separated fluid to obtain reinjection water; the flocculant is a cationic flocculant.
2. The method for treating drilling fluid waste liquid according to claim 1, wherein: the addition amount of the cationic flocculant is 5-10g/L.
3. The method for treating drilling fluid waste liquid according to claim 1, wherein: COD is less than or equal to 300mg/L after the electric flocculation treatment, and polyaluminium chloride is added during the air floatation treatment.
4. A method of treating drilling fluid waste liquid according to claim 3, wherein: the addition amount of the polyaluminum chloride is 1-5 g/L.
5. The method for treating drilling fluid waste liquid according to claim 1, wherein: COD after the electric flocculation treatment is more than 300mg/L, and polyaluminium chloride and polyacrylamide are added during air floatation treatment.
6. The method for treating drilling fluid waste liquid according to claim 5, wherein: the addition amount of the polyaluminum chloride is 3-4.5 g/L, and the addition amount of the polyacrylamide is 4-6 mg/L.
7. The method for treating drilling fluid waste liquid according to claim 1, wherein: the solid after the first solid-liquid separation is used for making bricks and/or paving well sites.
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