CN104438286A - Oil removing method of oil-base drilling cuttings - Google Patents
Oil removing method of oil-base drilling cuttings Download PDFInfo
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- CN104438286A CN104438286A CN201410647894.3A CN201410647894A CN104438286A CN 104438286 A CN104438286 A CN 104438286A CN 201410647894 A CN201410647894 A CN 201410647894A CN 104438286 A CN104438286 A CN 104438286A
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Abstract
The invention relates to an oil removing method of oil-base drilling cuttings. The method comprises the steps of feeding an emulsifying agent and acid into a solution of oily drilling cuttings, carrying out low-shear mixing for a period of time, and gradually separating hydrocarbon substances from the drilling cuttings to form small liquid drops, wherein the emulsifying agent has hydrophilia and comprises dispersed liquid drops, so that the effect of oil in water can be achieved; then, feeding active silicate, adjusting the pH value, and carrying out low-shear mixing to enable silicate to act with hydrogen ions to generate silicic acid, wherein silicic acid can be separated out from the solution due to the very low solubility; attaching silicic acid on the emulsified oil drops under the action of mixing to package the oil drops and form microcapsules, wherein the densities of the microcapsules are larger than the density of the solution, so that the microcapsules deposit at the bottom of the solution, and the aim of removing oil is achieved. According to the treatment method of the oil-base drilling fluid drilling cuttings, the cost is low, the oil removal rate is high and the technology is simple; according to the method, the problem of pollution caused by the drilling cuttings can be solved, the oil resources are recovered, and economical and effective innocent treatment is realized, and therefore, the oil removing method has a certain industrial popularization value.
Description
Technical field
The present invention relates to oil base drilling fluid drillings innoxious process for treating field, particularly relate to the sweep-out method of oil-contained drilling cuttings oil component.
Background technology
The main harmful constituent of oil base drilling fluid drillings is heavy metal ion, petroleum hydrocarbon, organic matter etc., ecological environment is had a strong impact on, and difficulty of governance is comparatively large, along with countries in the world are to environmental requirement increasingly stringent, oil base drilling fluid drillings harmless treatment has become instant thing.
All have strict regulation to drilling cuttings oil content abroad, Europe requires that from 1993 the content of oily substance in solid waste should be less than 1%, reaches zero-emission after in November, 2000.Although China does not also expressly provide drill waste mineral oil in fluid content standard, will be classified as hazardous waste containing mineral oil refuse, and control within 3000mg/kg dewatered sludge at agricultural sludge petroleum class content, require very strict.
Develop the technology of several treated drilling fluid drilling cuttings at present, comprise heat treating process (way of distillation), centrifugal separation, drilling cuttings cleaning technique, solvent extraction, burning method and biological treatment etc.Heat treatment costly; Drilling cuttings cleaning technique deoiling effect is limited, and can bring the process problem of oil-polluted water; Burning method needs burning facility, disposal cost costliness, and releases smoke pollution air; Petroleum resources in oil-contained drilling cuttings effectively do not utilize by biological treatment, treatment cycle is relatively long, and these methods all exist of poor benefits, the drawback such as cost is high, complex process.Therefore, from the angle of environmental protection and economic benefit, be necessary to find a kind of cost-effective oil-based drill cuttings process and oil recovery techniques.
Summary of the invention
In order to overcome the deficiency of oil-based drill cuttings process and oil recovery techniques in above-mentioned discussion, the invention provides a kind of oil-based drill cuttings deoiling method, it utilizes silicate chemistry under certain condition, physical characteristic realizes encapsulation to base oil, its density ratio solution is large, to be just deposited on bottom solution thus to reach oil removing object.
The invention discloses a kind of oil-based drill cuttings deoiling method: in the solution of oil-contained drilling cuttings, add emulsifying agent and acid, described emulsifying agent is 35% ~ 65% of drilling cuttings quality, and described acid is 20% ~ 40% of drilling cuttings quality; After carrying out low sheraing stirring, add active silicate, described silicate quality and drilling cuttings mass ratio are 0.2 ~ 0.8:1, pH is regulated to be 1 ~ 7, low sheraing stirs, the silicic acid formed is attached on emulsified oil droplet under the effect of stirring, and is encapsulated by oil droplet, forms microcapsules and to be deposited on bottom solution thus to reach oil removing object.Microcapsules dark circle core layer is packed drop, and outer transparent material is the capsule shell surface topography be made up of silicic acid, and its light transmittance is strong far beyond drop.
As preferably, regulate PH with one or more in potassium hydroxide, ammonium hydroxide.
In the present invention, described emulsifying agent is for comprising nonionic surface active agent and anionic surfactant, and the content of described nonionic surface active agent is 70-90%, and the content of described anionic surfactant is 10-30%.
Wherein, described nonionic surface active agent is the mixture of one or more arbitrary proportions in APES, AEO, fatty acid polyethylene glycol ester, polyol ester APEO and polyethers.
Described anionic surfactant is the mixture of one or more arbitrary proportions in neopelex, fatty alcohol-ether sodium sulfate, ethoxylated fatty-acid methyl ester sodium sulfonate, SAS, sodium alcohol ether carboxylate and alcohol ether sodium phosphate.
Described acid is the mixture of one or more arbitrary proportions in watery hydrochloric acid, dilute sulfuric acid, sulfurous acid, acetic acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, phosphoric acid.
Described active silicate is the mixture of one or more arbitrary proportions in sodium metasilicate, potassium silicate and ammonium silicate.
Oil-contained drilling cuttings oil removal treatment method cost of the present invention is low, oil removal rate is high, technique is simple, not only solves cuttings contamination problem, has also reclaimed petroleum resources, achieves economical and effective harmless treatment, has certain commercial introduction and is worth.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the invention will be further described:
Fig. 1 is the washing oil processing technology routine figure of the inventive method;
Fig. 2 is the silicate microcapsules oil removal process schematic diagram of the inventive method.
Detailed description of the invention
Below in conjunction with the embodiment in the present invention and accompanying drawing, be clearly and completely described the technical scheme in the embodiment of the present invention, obviously, described embodiment is only the present invention's part embodiment, instead of whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art, not making the every other embodiment obtained under creative work prerequisite, belong to the scope of protection of the invention.
1. the making of oil-contained drilling cuttings
Chose the carbonate rock 200g of 100 mesh sieves, with the 0# diesel oil Homogeneous phase mixing of 100mL, sealing, deposits in shady and cool place, leaves standstill filtration after 24 hours, room temperature is air-dry, obtain oil-contained drilling cuttings.
2. the configuration of emulsifying agent
This experiment nonionic surface active agent selects OP-10, and its HLB value is 14.5; Neopelex selected by anionic surfactant, and its HLB value is 10.638.The addition of surfactant and hydrochloric acid is in table 1.
The addition of surfactant and hydrochloric acid in table 1 embodiment 1-27
3. the drafting of calibration curve and the mensuration of drilling cuttings initial oil amount
Weighing 0.10g diesel oil with assay balance is dissolved in benzinum (60 ~ 90 DEG C), moves in the volumetric flask of 100mL, releases to graticule with benzinum (60 ~ 90 DEG C).Therefrom get its 20mL to be again positioned in 200mL volumetric flask, then use benzinum (60 ~ 90 DEG C) to release to graticule, obtain crude oil standard oil and use solution, mass concentration is 100mg/L.
In 100mL volumetric flask, add 100mL standard oil use solution, its concentration is 100mg/L; In the volumetric flask of 4 50mL, add 1 respectively, 5,10,15,20,30, the standard oil of 50mL uses solution, be diluted to graticule with benzinum (60 ~ 90 DEG C), corresponding concentration is respectively 1mg/L, 5mg/L, 10mg/L, 15mg/L, 20mg/L, 30mg/L, 50mg/L.At wavelength 225 ~ 254nm, use 10mm quartz colorimetric utensil, get benzinum (60 ~ 90 DEG C) and make reference liquid, the solution that an optional group configuration is good, draw maximum wavelength with measurement of ultraviolet-visible spectrophotometer.At selected maximum wavelength place, measure its absorbance, after blank correction, obtain the corresponding absorbance of crude oil, then draw crude oil calibration curve.Survey drilling cuttings initial oil amount, only drilling cuttings need be placed in distilled water carries out low sheraing stirring, then uses benzinum (60 ~ 90 DEG C) repeatedly to extract, and the absorbance of the oil product diluted after measuring extraction, reference standard curve, draws initial oil amount.Experimentally described in scheme, it is 0.952 that drilling cuttings only records absorbance through ultraviolet specrophotometer through emulsification treatment and extract after dilution.Obtaining drilling cuttings oil content as calculated is afterwards 1.119g.
4. the mensuration of oil removing experiment and oil removal rate
Adopt the processing technology routine shown in accompanying drawing 1, be uniformly dispersed by 4g oil-contained drilling cuttings, add surfactant and acid wherein by the amount in table 1 with 50mL distilled water, in agitator, low sheraing stirs, and hydrocarbons is separated gradually from drilling cuttings, forms droplet, emulsifying agent is hydrophily, and energy dispersant liquid drop, reaches oil-in-water effect, add active silicate (sodium metasilicate again, one or more in potassium silicate and ammonium silicate), keep silicate quality and drilling cuttings mass ratio between 0.2 ~ 0.8, with NaOH (or: potassium hydroxide, one or more in ammonium hydroxide) regulate pH to be 1 ~ 7, low sheraing stirs, silicate and hydrogen ion effect generate silicic acid, silicic acid solubility is very low, separate out from solution, be attached on emulsified oil droplet under the effect of stirring, oil droplet is encapsulated, forming microcapsules is deposited on bottom solution, filter out the microcapsules be deposited on bottom solution, reach oil removing object.Addition and the pH value of mixing time, active silicate see the following form:
The addition of mixing time, active silicate and pH value in table 2 embodiment 1-27
| Embodiment | Mixing time (min) | Active silicate (g) | PH value |
| 1 | 3 | 0.8 | 1 |
| 2 | 6 | 1.0 | 2 |
| 3 | 9 | 1.5 | 3 |
| 4 | 12 | 2.0 | 4 |
| 5 | 15 | 2.5 | 5 |
| 6 | 18 | 3.0 | 6 |
| 7 | 21 | 3.2 | 7 |
| 8 | 24 | 1.3 | 1 |
| 9 | 10 | 1.8 | 2 |
| 10 | 6 | 2.3 | 3 |
| 11 | 9 | 2.8 | 4 |
| 12 | 12 | 0.8 | 5 |
| 13 | 15 | 1.0 | 6 |
| 14 | 18 | 1.5 | 7 |
| 15 | 21 | 2.0 | 1 |
| 16 | 10 | 2.5 | 2 |
| 17 | 3 | 3.0 | 3 |
| 18 | 6 | 3.2 | 4 |
| 19 | 9 | 1.3 | 5 |
| 20 | 12 | 1.8 | 6 |
| 21 | 15 | 2.3 | 7 |
| 22 | 18 | 2.8 | 1 |
| 23 | 21 | 0.8 | 2 |
| 24 | 24 | 1.0 | 3 |
| 25 | 10 | 1.5 | 4 |
| 26 | 5 | 2.0 | 5 |
| 27 | 20 | 2.5 | 6 |
Remove in sedimental solution to above gained and add 20mL benzinum (60 ~ 90 DEG C) and repeatedly extract, carry out two-phase laminated flow with separatory funnel.Oil product after extraction is put into 50mL volumetric flask, in 100mL graduated cylinder, instills this solution of 1mL with glue head dropper, add benzinum (60 ~ 90 DEG C) and be diluted to 80mL benzinum (60 ~ 90 DEG C) and be diluted to 80mL place.In maximum absorption wave strong point, use 10mm cuvette, with benzinum (60 ~ 90 DEG C) for reference liquid, measure the absorbance of the rear solution of dilution.Reference standard curve, draws residual oil quality.Again according to the quality/drilling cuttings initial oil quality * 100% of oil removal rate=residual oil, draw oil removal rate.
The impact investigating different technology conditions oil removal rate draws, when the ratio of OP-10 and neopelex is 9:1, pH value is 2, and when mixing time is 10 minutes, oil removal rate is the highest, is 83.22%, and experiment deoiling effect is excellent.
Above-mentioned embodiment is intended to illustrate that the present invention can be professional and technical personnel in the field and realizes or use; modifying to above-mentioned embodiment will be apparent for those skilled in the art; therefore the present invention includes but be not limited to above-mentioned embodiment; any these claims or description of meeting describes; meet and principle disclosed herein and novelty, the method for inventive features, technique, product, all fall within protection scope of the present invention.
Claims (7)
1. an oil-based drill cuttings deoiling method, is characterized in that, adds emulsifying agent and acid in the solution of oil-contained drilling cuttings, and described emulsifying agent is 35% ~ 65% of drilling cuttings quality, and described acid is 20% ~ 40% of drilling cuttings quality; After carrying out low sheraing stirring, add active silicate, described silicate quality and drilling cuttings mass ratio are 0.2 ~ 0.8:1, pH is regulated to be 1 ~ 7, low sheraing stirs, the silicic acid formed is attached on emulsified oil droplet under the effect of stirring, and is encapsulated by oil droplet, forms microcapsules and to be deposited on bottom solution thus to reach oil removing object.
2. oil-based drill cuttings deoiling method according to claim 1, it is characterized in that, described emulsifying agent is for comprising nonionic surface active agent and anionic surfactant, the content of described nonionic surface active agent is 70-90%, and the content of described anionic surfactant is 10-30%.
3. oil-based drill cuttings deoiling method according to claim 2, it is characterized in that, described nonionic surface active agent is the mixture of one or more arbitrary proportions in APES, AEO, fatty acid polyethylene glycol ester, polyol ester APEO and polyethers.
4. oil-based drill cuttings deoiling method according to claim 2, it is characterized in that, described anionic surfactant is the mixture of one or more arbitrary proportions in neopelex, fatty alcohol-ether sodium sulfate, ethoxylated fatty-acid methyl ester sodium sulfonate, SAS, sodium alcohol ether carboxylate and alcohol ether sodium phosphate.
5. oil-based drill cuttings deoiling method according to claim 1, is characterized in that, described acid is the mixture of one or more the arbitrary proportion in watery hydrochloric acid, dilute sulfuric acid, sulfurous acid, acetic acid, hydrofluoric acid, hydrobromic acid, hydroiodic acid, phosphoric acid.
6. oil-based drill cuttings deoiling method according to claim 1, is characterized in that, described active silicate is the mixture of one or more arbitrary proportions in sodium metasilicate, potassium silicate and ammonium silicate.
7. oil-based drill cuttings deoiling method according to claim 1, is characterized in that, regulates pH with one or both in potassium hydroxide, ammonium hydroxide.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105107826A (en) * | 2015-09-15 | 2015-12-02 | 首钢京唐钢铁联合有限责任公司 | Disposal method for solid waste containing oil |
| CN105154124A (en) * | 2015-10-10 | 2015-12-16 | 山东大学 | Method for treating oily cuttings by adopting switch-type solvent |
| CN105618460A (en) * | 2015-12-30 | 2016-06-01 | 西南科技大学 | Degradation and solidification integrated treatment method for drillings containing oil |
| CN106281767A (en) * | 2016-08-11 | 2017-01-04 | 中国石油集团渤海钻探工程有限公司 | A kind of oil-contained drilling cuttings abluent and preparation method thereof |
| CN107881025A (en) * | 2017-10-17 | 2018-04-06 | 中海石油环保服务（天津）有限公司 | A kind of oil-based drill cuttings cleaning agent and its cleaning method |
| CN108296266A (en) * | 2018-02-01 | 2018-07-20 | 中国石油天然气集团有限公司 | A kind of drilling wastes processing system and method |
| CN109069894A (en) * | 2017-03-03 | 2018-12-21 | 美国傲世环保科技公司 | Using cohesion polymer system, micro- encapsulating handles asbestos fibre and other deleterious materials in situ |
| CN110157394A (en) * | 2019-05-21 | 2019-08-23 | 西安长庆化工集团有限公司 | A kind of drilling water packet oil anticalcium emulsifier and preparation method thereof |
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| CN105107826A (en) * | 2015-09-15 | 2015-12-02 | 首钢京唐钢铁联合有限责任公司 | Disposal method for solid waste containing oil |
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| CN105154124B (en) * | 2015-10-10 | 2016-10-26 | 山东大学 | A kind of method using switching mode solvent to process oil-contained drilling cuttings |
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| CN109069894A (en) * | 2017-03-03 | 2018-12-21 | 美国傲世环保科技公司 | Using cohesion polymer system, micro- encapsulating handles asbestos fibre and other deleterious materials in situ |
| CN109069894B (en) * | 2017-03-03 | 2021-07-06 | 美国傲世环保科技公司 | In situ microencapsulation treatment of asbestos fibers and other harmful materials using a combination of a copolymer and a coacervated polymer system |
| CN107881025B (en) * | 2017-10-17 | 2020-03-24 | 中海石油环保服务（天津）有限公司 | Oil-based drilling cutting cleaning agent and cleaning method thereof |
| CN107881025A (en) * | 2017-10-17 | 2018-04-06 | 中海石油环保服务（天津）有限公司 | A kind of oil-based drill cuttings cleaning agent and its cleaning method |
| CN108296266A (en) * | 2018-02-01 | 2018-07-20 | 中国石油天然气集团有限公司 | A kind of drilling wastes processing system and method |
| CN108296266B (en) * | 2018-02-01 | 2020-07-10 | 中国石油天然气集团有限公司 | Drilling waste treatment system and method |
| CN110157394A (en) * | 2019-05-21 | 2019-08-23 | 西安长庆化工集团有限公司 | A kind of drilling water packet oil anticalcium emulsifier and preparation method thereof |
| CN110157394B (en) * | 2019-05-21 | 2021-12-24 | 西安长庆化工集团有限公司 | Oil-in-water calcium-resistant emulsifier for well drilling and preparation method thereof |
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