CN1184150C - Process and apparatus for treating waste acidifying liquid in oil field - Google Patents
Process and apparatus for treating waste acidifying liquid in oil field Download PDFInfo
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- CN1184150C CN1184150C CN 00130274 CN00130274A CN1184150C CN 1184150 C CN1184150 C CN 1184150C CN 00130274 CN00130274 CN 00130274 CN 00130274 A CN00130274 A CN 00130274A CN 1184150 C CN1184150 C CN 1184150C
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- acid solution
- spent acid
- hydrogen peroxide
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Abstract
The present invention relates to a method and a device for the treatment of acid pickle acidified in oil (gas) fields. The method comprises the steps that hydrogen peroxide is added to acid pickle, and the mixture is stirred so that the molar concentration of hydrogen peroxide in a water body is 0.5 to 5 times as high as the original iron concentration in the acid pickle; alkali is added to adjust the pH so that the pH ranges from 5 to 9, and residual iron is removed; the treated acid pickle enters a solid-liquid separation device for solid-liquid separation. The device comprises a hydrogen peroxide chemical oxidation tank and the solid-liquid separation device which are sequentially connected with each other. The acid pickle treated by the method or the device reaches the national standards of outward discharge.
Description
Technical field
The present invention relates to the waste acidifying liquid in oil field treatment process.
Background technology
Along with the exploitation and the water filling of oil (gas, water) well, a large amount of rock cementing matters have been piled up near the stratum oil, the well, and these materials will stop up the stratum, cause oil well output decline and well water injection pressure to increase.Need acidifying (comprising pickling, matrix acidifying and fracture acidizing) to be carried out on the stratum in order to recover zone permeability, to improve oil well recovery ratio and water injection rate with acid solution.The oil field spent acid solution is meant and utilizes near the pollutent of acid solution removing at the bottom of oil, the well, recovers the rate of permeation on stratum or corrosion formation rock cementing matter and returns the residual acid solution that is discharged to ground when improving zone permeability.Acid solution commonly used in oil, the well acidifying has hydrochloric acid, mud acid, acetate, hybrid acid system etc., simultaneously in order to suppress the corrosion of acid solution to preparation of construction and pipeline, alleviates acidifying the stratum is produced new injury, improves acidifying efficient and need add certain chemical additive.Additive has: inhibiter, and to reduce corrosion to equipment and pipeline.Inhibiter commonly used has aldehydes, and sulfur-bearing class promoting agent contains oxygen class promoting agent.Iron stabilizer is to prevent iron class species precipitate.Anti-breast-emulsion splitter is used to abolish naturally occurring emulsifying agents such as bituminous matter, colloid and naphthenic acid to oil-external emulsion.
These return and are discharged to the ground spent acid solution, contain many residual acid and acidizing additive, also carry some drop table matter, colloid, naphthenic material simultaneously from the stratum.Spent acid solution has the low pH1 of acidity～2, and the high 150～1000mg/l of concentration of iron above (mainly containing ferrous ion) contains the characteristics about organic material (TOC) 100mg/l.
Handle the oilfield waste acid solution at present both at home and abroad and mainly adopt neutralization---Coagulation Method.At first add a certain amount of alkali lye and neutralize in returning acid discharge liquid, alkali lye mainly contains NaOH, Na
2CO
3, lime and Ca (OH)
2Add certain coagulating agent behind the neutralization precipitation again, wherein, carry out coagulating sedimentation, the supernatant liquor discharging based on polymeric aluminum, polyacrylamide.This kind method processing spent acid solution can in time neutralize spent acid solution and through removing the suspended particle more than 95% behind the coagulation, reach the purpose of neutralization discharging.But this treatment process, the mud generation is big, generally accounts for the 30%-40% of flooding quantity, contains the mud water ratio up to 99%, and settling velocity slow (generally needing just can settle out in 2-5 hour), and is not high to the organic substance clearance, water outlet Fe
2+Concentration height, and the easy oxidized back formation particulate matter of the ferrous iron in the water outlet make the effluent quality variation, are unfavorable for discharging and utilization again.Because the mud generation is bigger, the sludge treatment cost is higher.
Summary of the invention
In order to overcome above-mentioned shortcoming, present method inventor becomes ferric iron with oxidation of divalent to finding in the spent acid solution research rapidly when adding the peroxidation Hydrogen Energy in certain spent acid solution pH scope, thereby reaches the purpose of removal.Simultaneously, the peroxidation Hydrogen Energy decomposites the very strong hydroxyl radical free radical of oxidation capacity rapidly organic substance is oxidized to oxy-compound or the carboxylic compound that easily is adsorbed, and partial organic substances is direct oxidation into carbonic acid gas and water.When re-adjustment pH ferric iron hydrolysis to the certain limit is formed with the hydrated iron of strong adsorptive power and with oxidized pollution substances such as organic substance absorption, removes organic substance and ferrous iron makes water outlet purpose up to standard thereby reach.Its reaction formula is:
…
Treatment process: hydrogen peroxide oxidation---(regulate pH to certain limit carry out sedimentation)---pH regulator neutrality (and aeration)---solid-liquid separation operation steps (seeing accompanying drawing 1) is:
1. add hydrogen peroxide in spent acid solution, the 0.5-5 that to make its volumetric molar concentration in the mixed solution of spent acid solution and hydrogen peroxide be original ferrous iron concentration in the spent acid solution doubly stirs for some time with the commentaries on classics whipping device.Time to stirring has no particular limits, but best more than 10 minutes.Make most of ferrous iron be oxidized to ferric iron and organic substance is produced adsorption, decomposite a large amount of hydroxyl radical free radicals simultaneously, organic substance in the oxidation water body.The 2-4 that it is original ferrous iron concentration in the spent acid solution that the amount of the hydrogen peroxide that adds in spent acid solution preferably makes its volumetric molar concentration in the mixed solution of spent acid solution and hydrogen peroxide doubly.
2. add alkali and regulate between the pH to 5 and 9, preferably carry out aeration, residual iron is removed.
3. spent acid solution after treatment enters solid-liquid separating equipment, carries out solid-liquid separation.The solid-liquid separation pattern can be settlement separate, centrifuging, Plate Filtration, membrane filtration, quartz sand filtration, or fiber filter.
4. when ferrous iron in the water body and organic concentration are higher, need to add the hydrogen peroxide of big concentration to carry out oxidation.After oxidation was finished, owing to residual in the spent acid solution hydrogen peroxide arranged, as directly pH regulator to neutrality being caused the mud come-up, solid-liquid separation effect was bad.For this spent acid solution, need after oxidation, to carry out precipitate and separate, and then finish following steps (seeing accompanying drawing 2).
In aforesaid method, in spent acid solution, add hydrogen peroxide and carry out before the oxidation or in the adition process, the most handy alkali is regulated pH to 2.5-4.5, makes spent acid solution reach oxidized preferably scope.Best results when preferably regulating pH to 3.0-3.5.
The spent acid solution treatment unit: this device is to be the treatment unit that sequencing makes up with " add hydrogen peroxide oxidation--solid-liquid separation ".Comprise various pH regulator devices in this device, hydrogen peroxide adds control device, chemical oxidation device, precipitation separation device, air aeration device and equipment for separating liquid from solid.Treatment unit can be a continous way, also can be step.Continous way simple to operate be suitable for handling big liquid measure, but facility investment is bigger, and step facility investment is less, but troublesome poeration, is suitable for handling the water yield when less.
Thereby, the present invention also provides a kind of spent acid solution treatment unit, comprise hydrogen peroxide chemical oxidation pond and solid-liquid separating equipment that order links to each other, between two above-mentioned equipment, preferably also connect an air aeration equipment, on the hydrogen peroxide chemical oxidation pond, connect a hydrogen peroxide and add control device, and preferably also be connected with a pH on-line monitoring control medicine machine, on air aeration equipment, connect a pH on-line monitoring equipment.In equipment of the present invention, between hydrogen peroxide oxidation pond and air aeration equipment, can also connect a precipitate and separate pond, connected a pH on-line monitoring equipment on this precipitate and separate pond.
The present invention is with advanced oxidation, pH control and atmospheric oxidation, the integrated combination process of solid-liquid separation and device, spent acid solution can reach standard outside the country after this method is handled, for the processing that solves the acidification of oil field waste liquid makes it the innovation of qualified discharge tool uniqueness, water outlet can reach national wastewater disposition standard fully.
Brief Description Of Drawings
Fig. 1 is the synoptic diagram of acidifying liquid waste treating apparatus of the present invention;
Fig. 2 is the synoptic diagram of another embodiment of acidifying liquid waste treating apparatus of the present invention.
Embodiment 1: low concentration peroxide dosage is handled waste acidifying liquid in oil field treatment process and device
Embodiment 1 is one of embodiment of the present invention (seeing accompanying drawing 1).Come water water quality: ferrous iron 208mg/l, total iron 213mg/l, TOC 91.4mg/l, pH1.4,135 ° of colourities.Handle this spent acid solution and will pass through following four steps.(1) be under the stirring of 50RPM at rotating speed, the sodium hydroxide adjusting pH to 3.28 (2) that adds 10mol/l adds 3% H under rotating speed 50RPM
2O
2Making its concentration is 180mg/l, carries out the reaction of Fenton reagent oxidation, and the reaction times is 45min.(3) add alkali and regulate pH to neutral, carry out solid-liquid separation, produce a large amount of ferric hydroxide precipitate, sludge quantity accounts for 10% of flooding quantity.(4) water outlet machine aeration 15min carries out atmospheric oxidation, removes remaining iron ion.Find out that from Inlet and outlet water water quality water quality has reached country and effluxed standard.Available precipitation separation, centrifugation, filtration, Plate Filtration or the membrane filtration etc. of solid-liquid separation.
The acidifying liquid waste treating apparatus is handled back water quality situation
| Project | pH | TOC(mg/l) | Fe 2+(mg/l) | Total Fe (mg/l) | Colourity | Mud amount (%) |
| Come water | 1.4 | 91.5 | 208 | 213 | 135 | |
| Water outlet | 6.8 | 43 | 0.1 | 0.3 | 30 | ＜10 |
(annotate: pH is measured by acidometer.TOC is measured by the TOC determinator.Ferrous iron is by adjacent coffee colorimetric method for determining.Total iron is by atomic absorption detecting.Colourity is by colorimetric method for determining.High 2-8 * 10 of arriving of chlorine root because of the acidifying waste liquid
4Mg/l can't measure the value of chemical oxygen demand (COD) in the water body (COD).TOC (total organic carbon) can accurately reflect organic content in the water body, and COD is 2.4-3.0 with the ratio of TOC.)
Embodiment 2: higher concentration hydrogen peroxide dosage is handled waste acidifying liquid in oil field treatment process and device
Come water water quality: ferrous iron 808mg/l, total iron 873mg/l, TOC 291mg/l, pH1.5,165 ° of colourities.Adopt in embodiment 1 processing and find, when add the 1500mg/l hydrogen peroxide carry out oxidation after, regulate pH and after neutrality is carried out air aeration, carry out solid-liquid separation, owing to produce a large amount of bubbles after the oxidation after the residual concentration hydrogen peroxide decomposition, cause the settleability of mud very poor, inaccessible solid-liquid separation.After finishing, stage oxidation carries out precipitate and separate, processed liquid pH to 5.5 after the adjusting oxidation, and solid-liquid separation effect is better.Processed liquid through in and aeration and filter after waste liquid can reach national wastewater disposition standard.
Treatment unit is handled back water quality situation
| Project | pH | TOC(mg/l) | Fe 2+(mg/l) | Total Fe (mg/l) | Colourity | Mud amount (%) |
| Come water | 164 | 291 | 808 | 873 | 165 | |
| Water outlet | 6.8 | 40 | 0.1 | 0.3 | 30 | ＜10 |
Claims (7)
1. waste acidifying liquid in oil field treatment process may further comprise the steps:
(1) in spent acid solution, add hydrogen peroxide and stirring, to make its volumetric molar concentration in the mixed solution of spent acid solution and hydrogen peroxide be original ferrous iron concentration in the spent acid solution 0.5-5 times;
(2) add alkali and regulate between the pH to 5 and 9, residual iron is removed;
(3) spent acid solution after treatment enters solid-liquid separating equipment, carries out solid-liquid separation.
2. in accordance with the method for claim 1, wherein, the volumetric molar concentration of hydrogen peroxide in the mixed solution of spent acid solution and hydrogen peroxide that adds in the step (1) is 2-4 times of original ferrous iron concentration in the spent acid solution.
3. in accordance with the method for claim 1, wherein, add hydrogen peroxide in spent acid solution before or in the adition process, the pH with alkali adjusting spent acid solution carries out oxidation in the scope of pH 2.5-4.5.
4. in accordance with the method for claim 1, wherein, in step (2), add and carry out the aeration processing after alkali is regulated between the pH to 5 and 9.
5. in accordance with the method for claim 1, wherein, the solid-liquid separation pattern in the step (3) is settlement separate, centrifuging, Plate Filtration, membrane filtration, quartz sand filtration, or fiber filter.
6. in accordance with the method for claim 3, wherein, in the step (1) with pH regulator to 3.0-3.5.
7. according to any described method in the claim 1 to 6, wherein, after the oxidation of step (1) is finished, carry out precipitate and separate, and then carry out following steps.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00130274 CN1184150C (en) | 2000-11-02 | 2000-11-02 | Process and apparatus for treating waste acidifying liquid in oil field |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 00130274 CN1184150C (en) | 2000-11-02 | 2000-11-02 | Process and apparatus for treating waste acidifying liquid in oil field |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1353090A CN1353090A (en) | 2002-06-12 |
| CN1184150C true CN1184150C (en) | 2005-01-12 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 00130274 Expired - Lifetime CN1184150C (en) | 2000-11-02 | 2000-11-02 | Process and apparatus for treating waste acidifying liquid in oil field |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102107942B (en) * | 2009-12-25 | 2014-09-24 | 安集微电子（上海）有限公司 | Processing method of chemical mechanical polishing (CMP) waste liquid |
| CN102417256A (en) * | 2011-10-20 | 2012-04-18 | 无锡君隆环保设备有限公司 | Advanced treatment method for chemical fiber pulp sewage |
| US9677392B2 (en) * | 2012-06-25 | 2017-06-13 | Signa Chemistry, Inc. | Use of metal silicides in hydrocarbon production and transportation |
| CN104948138B (en) * | 2015-04-28 | 2018-02-06 | 中石化石油工程设计有限公司 | The on-line checking and processing method and system of a kind of acidifying solution |
| CN105060555A (en) * | 2015-07-29 | 2015-11-18 | 中国石油化工股份有限公司 | Online reusing and processing technology of water well acidified flowback fluid |
-
2000
- 2000-11-02 CN CN 00130274 patent/CN1184150C/en not_active Expired - Lifetime
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| CN1353090A (en) | 2002-06-12 |
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