CN1156408C - Process and equipment for treating sewage in oil field - Google Patents
Process and equipment for treating sewage in oil field Download PDFInfo
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- CN1156408C CN1156408C CNB001336029A CN00133602A CN1156408C CN 1156408 C CN1156408 C CN 1156408C CN B001336029 A CNB001336029 A CN B001336029A CN 00133602 A CN00133602 A CN 00133602A CN 1156408 C CN1156408 C CN 1156408C
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Abstract
The present invention provides a method for treating sewage of oil production in oil fields, which comprises: regulating the pH value of the sewage of oil production to 3.0 to 6.0, adding divalent ferric salts and strong oxidants and separating solid and liquid, wherein the molar concentration ratio of the ferrous iron to the strong oxidants is from 0.5 to 5, and the addition of ferrous iron is from 0.2 to 4 times of COD to be removed. The present invention also provides a device used for treating sewage of oil production in oil fields.
Description
The present invention relates to be used for method and the device that oilfield produced water is handled.
Also need inject a large amount of water and steam from stratum extraction many local waters, particularly oilfield exploitation to the middle and later periods in order to improve output in the exploitation of oil (gas) well, crude oil water content is risen, the sewage generation increases.Oil extraction-generated waste water is meant the sewage that produces in oil (gas) the well recovery process, and this sewage contains emulsified crude oil, disperses crude oil and height emulsified crude oil, the soil ulmin in the stratum, naphthenic acid, formation shut-off material (as dodecane sulfonate), crude oil demulsifier etc.
The oil extraction-generated waste water of deviating from from crude oil has following characteristics: oleaginousness height: 500-1000mg/l, chemical oxygen demand (COD): 500-800mg/l, contains a certain amount of suspended substance 200-500mg/l by the high 50-75 of water temperature ℃.
Handle oilfield produced water at present both at home and abroad and mainly adopt following treatment process:
1. coagulation---filtration method
Effusive sewage comes water to filter through gravity settling (or inclined plate sedimentation)---coagulant precipitation---in the dehydrating of crude oil equipment.
2. coagulation---air supporting---filtration method
Dehydrating of crude oil comes water to filter through gravity settling (or inclined plate sedimentation)---air supporting---.
3. coagulation---air supporting---biochemical treatment
To from gravity settling (or inclined plate sedimentation)---air supporting---biochemical treatment.
About the oil extraction-generated waste water oil-containing 10mg/l after method 1 and 2 is handled, chemical oxygen demand (COD) (COD
Cr) 300-500mg/l.Because the oil extraction waste water biodegradability is relatively poor, utilizes the very difficult of biochemical treatment, generally all need handle through anaerobic-aerobic, about sewage with oil 5mg/l after treatment, chemical oxygen demand (COD) 150-200mg/l.Simultaneously because oilfield sewage comes the water complexity, and it is very big to change when utilizing the biochemical treatment running greatly difficulty, causes water outlet often to exceed standard, and is difficult to satisfy the standard that effluxes.In addition, many oily(waste)water biodegradability extreme differences can't be used biochemical treatment.
In order to overcome above-mentioned shortcoming, present method inventor adopts reaction to adsorb---and the oxidative treatment oil extraction waste water can reach the good treatment effect.Oil extraction-generated waste water behind coagulation is regulated and is added a certain amount of divalent iron salt and hydrogen peroxide behind certain pH value, and ferrous ion can be generated ferric iron by oxidation rapidly, and the complex compound that the ferric iron hydrolysis generates has very strong energy-absorbing power, organism can be adsorbed.Hydrogen peroxide produces the very strong hydroxyl radical free radical of a large amount of oxidation capacities under ferrous iron catalysis simultaneously, oxidation operation can be decomposed, or it is carried out chemical modification, makes it be easy to be adsorbed by ferric iron hydrolytic precipitation thing.
An object of the present invention is to provide a kind of method that oilfield produced water is handled that is used for.
Another object of the present invention provides a kind of equipment that oilfield produced water is handled that is used for.
The invention provides a kind of oilfield produced water treatment process, comprise: a kind of oilfield produced water treatment process, comprise: with the pH regulator of oil extraction-generated waste water is 3.0-6.0, add divalent iron salt and strong oxidizer, the molar concentration rate of ferrous iron and strong oxidizer is 0.5-5, ferrous add-on is to wait to remove 0.2 to 4 times of COD, carries out solid-liquid separation then.
In aforesaid method of the present invention, described solid-liquid separation is carried out under acidic conditions, then neutralization.Described strong oxidizer is meant that standard potential is 1.0 volts of above oxygenants, hydrogen peroxide, chlorine, the oxymuriate, and/or ozone of comprising commonly used in water treatment.Ferrous add-on generally should be 0.2 to 4 times of waiting the to remove COD ratio of the weight of COD (weight of iron ion with).This addition requires to become according to different water quality and water outlet.In general, the water outlet COD value that requirement reaches is low more, and ferrous addition is many more.
When former water contains the oil of higher concentration and COD, carry out once the back with the method for coagulation-solid-liquid separation and carry out oxidation-absorption reaction adding under ferrous iron and the condition of strong oxidizer, carry out solid-liquid separation then at pH3.0-6.0.The coagulating agent that pre-treatment is used comprises various molysite or aluminum salt.
In the method for the invention, described strong oxidizer is hydrogen peroxide preferably, and the treatment time of ferrous iron and strong oxidizer is preferably more than 1 hour.
In the method for the invention, the described solid-liquid separation of carrying out under acidic conditions can be settlement separate or dissolved air flotation.In order to reach treatment effect preferably, hydrogen peroxide and ferrous treatment time were preferably in more than 1 hour, got final product in 1 to 5 hour generally speaking.Described divalent iron salt can be the water-soluble any divalent iron salt of energy.
In the method for the invention, be preferably in and carry out under the acidic conditions carrying out aeration after solid-liquid separation and the neutralization, carry out solid-liquid separation again.
The present invention also provides a kind of equipment that oilfield produced water is handled that is used for, comprise absorption-oxidation pond that order links to each other, solid-liquid separating equipment and neutralization tank, wherein, be connected with the pH Online Monitoring Control on the absorption-oxidation pond and add dose equipment, hydrogen peroxide dosage operating device and divalent iron salt dosage operating device; Be connected with the pH Online Monitoring Control on the neutralization tank and add dose equipment.
In equipment of the present invention, described neutralization tank be preferably have concurrently aeration performance in and the aeration tank.
The present invention is with reaction absorption, chemical oxidation, pH control and atmospheric oxidation, the integrated combination process of solid-liquid separation, oil production waste water in oil field can reach standard outside the country after this method is handled, for solving the innovation of oil production waste water in oil field qualified discharge tool uniqueness, water outlet can reach national wastewater disposition standard fully.Reaction absorption-oxidation processing technique is to utilize the ferric iron that forms in the reaction, forms complex compound under hydrolytic action, and good adsorptivity is arranged, and the hydroxyl that the while hydrogen peroxide decomposition goes out can carry out oxidation to organism, strengthens organic adsorptivity.
Brief Description Of Drawings
Fig. 1 is the synoptic diagram of oil extraction waste water treatment unit of the present invention.
Example 1: reaction absorption---chemical oxidation treatment oil extraction waste water treatment method
Come water water quality: TOC258mg/l, pH7.6, COD
Cr603mg/l, petroleum-type: 80mg/l.Handle this spent acid solution and will pass through following four steps.(1) be under the stirring of 100RPM at rotating speed, 100ppm (v/v) polymerization iron carries out coagulation, and sedimentation 1 hour.(2) add ferrous sulfate under rotating speed 100RPM, making its concentration is 100mg/l, adds 3% H simultaneously
2O
2Making its concentration is 50mg/l, carries out the adsorption and oxidation reaction, and the reaction times is 120min.(3) settling time is 30 minutes, and solid-liquid separation is carried out in water outlet.(4) through the sewage of solid-liquid separation regulate pH value be 8.0 and aeration 15min carry out atmospheric oxidation, remove remaining iron ion.Find out that from effluent quality water quality has reached country and effluxed standard.
The acidifying liquid waste treating apparatus is handled back water quality situation
Project PH TOC (mg/l) COD
CrMg/l) mud amount (%)
Come water 7.6 258 603
Water outlet 6.8 40 100＜2
(annotate: PH adopts glass electrode method to be measured by acidometer.TOC is measured by the TOC500 determinator, COD
CrThe employing potassium dichromate process is measured.)
Embodiment 2: reaction absorption---chemical oxidation treatment oil extraction waste water treatment method
Come water water quality: TOC 129mg/l, pH7.5, COD
Cr260mg/l.At first PH is adjusted to 4.5, adds ferrous sulfate and hydrogen peroxide, and its concentration is respectively: 50mg/l and 24mg/l, carry out chemical oxidation.After oxidation in 3 hours, carry out solid-liquid separation.Transfer to neutral also aeration 15min at last and remove residual iron.
Treatment unit is handled back water quality situation
Project PH TOC (mg/l) COD
Cr(mg/l) mud amount (%)
Come water 7.6 129 260
Water outlet 8.0 37 114＜2
Embodiment 3
According to embodiment 1 described step, trivalent iron salt coagulation effect and different concns react absorption-chemical oxidizing agent treatment effect down under the mensuration different concns, obtain following result.
From table 1 and table 2 as can be seen, compare with the ferric iron coagulating agent, treatment effect of this reaction absorption-chemical oxidizing agent effect is better.
Table 1: trivalent iron salt coagulation effect under the different concns
| Fe 3+ | 0 | 50 | 100 | 200 |
| COD crmg/l | 260 | 210 | 195 | 180 |
Table 2: different concns is reaction absorption-chemical oxidizing agent treatment effect down
| Fe 2+(mg/l) | 0 | 50 | 100 |
| H 2O 2(mg/l) | 0 | 23 | 46 |
| COD crmg/l | 260 | 125 | 100 |
Claims (9)
1. oilfield produced water treatment process comprises:
With the pH regulator of oil extraction-generated waste water is 3.0-6.0, adds divalent iron salt and strong oxidizer, and the ferrous ion in the divalent iron salt and the molar concentration rate of strong oxidizer are 0.5-5, and the ferrous ion add-on in the divalent iron salt is to wait to remove 0.2 to 4 times of COD;
Carry out solid-liquid separation then.
2. in accordance with the method for claim 1, wherein said solid-liquid separation is carried out under acidic conditions, then neutralization.
3. in accordance with the method for claim 1, wherein, described strong oxidizer is a hydrogen peroxide, chlorine, oxymuriate, and/or ozone.
4. in accordance with the method for claim 1, wherein, described strong oxidizer is a hydrogen peroxide.
5. in accordance with the method for claim 1, before oil extraction-generated waste water is handled, carry out coagulation and solid-liquid separation earlier.
6. in accordance with the method for claim 1, wherein, the ferrous ion in the divalent iron salt and the reaction times of strong oxidizer are more than 1 hour.
It is 7. in accordance with the method for claim 2, wherein said that to carry out solid-liquid separation under acidic conditions be settlement separate or dissolved air flotation.
8. in accordance with the method for claim 1, wherein, the ferrous ion in the divalent iron salt and the molar concentration rate of strong oxidizer are 0.5-1.0.
9. in accordance with the method for claim 1, wherein, under acidic conditions, carry out carrying out aeration after solid-liquid separation and the neutralization, carry out solid-liquid separation again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001336029A CN1156408C (en) | 2000-11-28 | 2000-11-28 | Process and equipment for treating sewage in oil field |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB001336029A CN1156408C (en) | 2000-11-28 | 2000-11-28 | Process and equipment for treating sewage in oil field |
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| Publication Number | Publication Date |
|---|---|
| CN1355143A CN1355143A (en) | 2002-06-26 |
| CN1156408C true CN1156408C (en) | 2004-07-07 |
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| Application Number | Title | Priority Date | Filing Date |
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| CNB001336029A Expired - Lifetime CN1156408C (en) | 2000-11-28 | 2000-11-28 | Process and equipment for treating sewage in oil field |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1300017C (en) * | 2005-04-14 | 2007-02-14 | 哈尔滨工业大学 | Tech. process for reducing mineralization of extracting oil sewage |
| CN101186402B (en) * | 2007-11-27 | 2011-06-01 | 华泰集团有限公司 | Fenton two-stage method oxidation processing technique for paper-making and pulping waste water |
| CN102030435B (en) * | 2009-09-30 | 2012-12-05 | 北京中科国益环保工程有限公司 | Method for treating oil field drilling waste water |
| CN102115283B (en) * | 2011-01-20 | 2012-04-11 | 哈尔滨商业大学 | Method for treating wastewater from oil extraction |
| CN104310561A (en) * | 2014-11-24 | 2015-01-28 | 天津大港油田滨港集团博弘石油化工有限公司 | Ferrous ion treating agent for oil production |
| CN108249621A (en) * | 2018-01-31 | 2018-07-06 | 金碳环境科技（天津）有限公司 | A kind of oil-containing sewage treatment technique |
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2000
- 2000-11-28 CN CNB001336029A patent/CN1156408C/en not_active Expired - Lifetime
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