CN102313658B - Method for preparing naphthenic acid sample in wastewater - Google Patents
Method for preparing naphthenic acid sample in wastewater Download PDFInfo
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- CN102313658B CN102313658B CN201010222011.6A CN201010222011A CN102313658B CN 102313658 B CN102313658 B CN 102313658B CN 201010222011 A CN201010222011 A CN 201010222011A CN 102313658 B CN102313658 B CN 102313658B
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Abstract
The invention discloses a method for preparing a naphthenic acid sample in petroleum wastewater. The method comprises the following steps of: adjusting a wastewater sample to be acid, and adsorbing acid and neutral organic matters in the wastewater sample by using an adsorption resin column; backwashing the resin column subjected to adsorption by using alkali liquor, and eluting an acid organic matter; making a backwashing solution pass through an H-type cation exchange resin column, evaporating the passed solution in a rotating way, freeze-drying, and thus obtaining a small molecule naphthenic acid solid sample; and backwashing precipitates on the H-type cation exchange resin column by using the alkali liquor, adjusting the pH value of the backwashing solution to be less than or equal to 2 by using hydrochloric acid, standing, collecting the precipitates, and recycling a macromolecule naphthenic acid solid sample from the precipitates. By the method, the mass of the small molecule naphthenic acid solid sample or the macromolecule naphthenic acid solid sample is tested respectively to determine the content of the two samples in the wastewater, and the molecular weight and the structural features of naphthenic acid can be represented by an element analysis and solid 13C nuclear magnetic resonance method, a Fourier infrared spectrum method and an atmospheric pressure ionization mass spectrometry.
Description
Technical field
The present invention relates to a kind of separation and sample preparation methods of measuring naphthenic acid in waste water, be applicable to enrichment, separation and the sample preparation of naphthenic acid in all kinds of oil refining or oil field waste, be particularly useful for the electro-desalting waste water of refinery processing highly acid crude oil, produce the oil field extracted water of high-acid crude oil, containing extraction and the preparation of naphthenic acid in alkali polymer flooding water and oil-sand extraction pitch technique waste water, the sample of preparation can be used for naphthenic acid content, molecular weight distribution or structural characterization.
Background technology
Naphthenic acid is that alkyl replaces complex mixture acyclic or that alkyl-substituted alicyclic carboxylic acid forms, it is the natural constituents of oil, can enter into oil field extracted water or refinery(waste) water by production and the processing of crude oil, as produce high-acid crude oil oil field extracted water, containing alkali polymer flooding water, refinery processing highly acid crude oil electro-desalting waste water and oil-sand extraction pitch technique waste water etc., conventionally contain the naphthenic acid of higher concentration.
The molecular weight of naphthenic acid is generally 100～1300, contains monobasic～quaternary carboxyl.Monobasic naphthenic acid is more common, and molecular weight is 100～600,250～350 ℃ of boiling points, and pKa 5～6, and general molecular formula is C
nh
2n+Zo
2, in formula, n is carbon number, and Z is hydrogen degree of unsaturation, is 0 or negative even number, and-Z/2 is the quantity of ring.The difficult volatilization of naphthenic acid, stable chemical nature, has surfactivity, and its sodium salt is soluble in water.The corrosivity of naphthenic acid is a difficult problem for puzzlement field produces always, and high molecular naphthenic acid interfacial activity is stronger, and its slaine easily deposits, and affects the normal operation of oil-water separator.Naphthenic acid is difficult to biochemical degradation, is the key component that affects high acid crude oil electric desalting wastewater and contain alkali polymer flooding water qualified discharge.Naphthenic acid is one of component that refinery(waste) water Poisoning is the strongest, toxic to hydrobiont, and low-molecular-weight naphthenic acid toxicity is stronger.
In waste water, the analysis of naphthenic acid is its prerequisite of evaluating, controlling and administer with characterizing, and because naphthenic acid is that a class character extremely approaches, forms extremely complicated homolog, the method that there is no is so far isolated single naphthenic acid component.In water, naphthenic acid generally adopts under acid condition under solvent extraction or acid condition solvent under solvent extraction-alkali lye back extraction-acid condition to extract pre-service again, then with gravimetric method, acid base titration, Fourier transform infrared spectrometry, derivative-vapor-phase chromatography, derivative-GC-MS, atmospheric pressure ionization (electron spray or atmospheric pressure chemical ionization) mass spectrometric determination, conventional extraction solvent comprises sherwood oil, methylene chloride, methenyl choloride and phenixin etc.
In said determination method, gravimetric method, acid base titration, Fourier transform infrared spectrometry can be measured naphthenic acid content in waste water, but sensitivity and selectivity are poor; Derivative-vapor-phase chromatography or derivative-GC-MS is limited to derivative efficiency, and gas chromatography is difficult to analyze high molecular naphthenic acid derivant; Atmospheric pressure ionization (electron spray or atmospheric pressure chemical ionization) mass spectroscopy only can qualitative analysis naphthenic acid.In waste water, the content of naphthenic acid, molecular weight distribution and structural characterization need the multiple analysis means of integrated use, need to be from waste water high efficiency extraction or prepare a certain amount of high-purity naphthenic acid sample.
Solvent extraction is difficult to prepare the high-purity sample of the required q.s of the comprehensive Spectroscopic Characterization of naphthenic acid from low concentration naphthenic acid waste water, because non-solvent organic carbon in water sample after solvent extraction is difficult to measure, makes the extraction efficiency of naphthenic acid also be difficult to assessment.
Summary of the invention
For the deficiencies in the prior art, the invention provides separation and the sample preparation methods of naphthenic acid in a kind of oil industry wastewater, the enrichment times of naphthenic acid of the present invention and the recovery are all higher, the naphthenic acid recovery is not less than 85%, the purity of preparing naphthenic acid is good, and preparation amount meets the needs of naphthenic acid comprehensive characterization completely.
Preparation method's process of naphthenic acid sample in wastewater of the present invention is as follows:
(1) wastewater sample is adjusted to after acidity, by adsorption resin column, adsorbs acidity and Neutral Organic Compound wherein, and polymeric adsorbent is styrene-divinylbenzene polymer resin;
(2) the resin column alkali lye backwash after absorption, with the acid organism of wash-out;
(3) backwash liquor is by H type cation exchange resin column, and the solution passing through, through rotary evaporation and freeze-drying, obtains little molecular naphthenic acid solid sample;
(4) the sediment alkali lye backwash on H type cation exchange resin column, backwash liquor is less than or equal to 2 with hydrochloric acid adjust pH, standing and collecting precipitation thing, sediment is after filtration, after cleaning, centrifugal, freeze-drying, obtain large molecular naphthenic acid solid sample;
(5) quality of measuring respectively little molecule or large molecular naphthenic acid solid sample is determined its content in waste water, and the sample of preparation can further be used molecular weight and the architectural feature of the characterized by techniques naphthenic acid such as ultimate analysis, solid-state 13C nuclear magnetic resonance method, Fourier transform infrared spectrometry and atmospheric pressure ionization mass spectroscopy.Measure total organic carbon that detachment process respectively walks sample and can determine the recovery of pretreated efficiency and naphthenic acid.
The sorting technique of above-mentioned large molecular naphthenic acid and little molecular naphthenic acid is: large molecular naphthenic acid is water insoluble under acid condition, i.e. insoluble naphthenic acid, little molecular naphthenic acid all water soluble, i.e. solubility naphthenic acid under pH arbitrarily.
The specification of adsorption resin column and resin admission space change and determine with the volume of water sample of processing and organic concentration, and typical adsorption resin column is the glass column of long 700mm, internal diameter 40mm, resin admission space 800mL.Resin column filler is styrene-divinylbenzene polymer resin, as Amberlite DAX-8 resin.Before resin filling, need to purify, the purification method of reference is: 0.1mol/L NaOH soaks 24h, then uses washed with de-ionized water, to remove remaining NaOH; Resin after cleaning extracts and is not less than 16h by each Soxhlet of methylene chloride, acetone and methyl alcohol successively.Resin after purification is packed in glass column, the two ends useable glass of resin extender is continuous fixing, then use successively deionized water, 0.1mol/L NaOH, deionized water, 0.1mol/L HCl and washed with de-ionized water, until the total organic carbon of eluent (TOC) is lower than 1.0mg/L.
The specification of H type cation exchange resin column is identical with adsorption resin column or similar with resin admission space, and filler is H type Zeo-karb, as MTO-Dowex Marathon MSC H Form Zeo-karb.Before resin filling, need to purify, available methyl alcohol Soxhlet is extracted and is not less than after 16h, MSCH Form Zeo-karb after purification packs in glass column, the two ends useable glass of resin extender is continuous fixing, then use successively deionized water, 0.1mol/L NaOH, deionized water, 0.1mol/L HCl and washed with de-ionized water, until the TOC of eluent is lower than 0.5mg/L.Now MSC H Form cation exchange resin column is H
+saturation type.
A kind of concrete operation method of the present invention is as follows: after the abundant settling suspension solid of waste water, get 0.5～50L upper strata clear water, with HCl, adjust pH≤2, then the flow velocity with 10～25mL/min passes through DAX-8 adsorption resin column, measures the TOC of effluent.The remaining sample of washed with de-ionized water of 2～5 times of polymeric adsorbent bed volume for adsorption resin column after absorption, next uses sig water (as the 0.1mol/L NaOH) backwash of 5～8 times of polymeric adsorbent bed volume, measures the TOC of backwash liquor.The organism that backwash is got off is naphthenic acid sodium salt, comprises large molecular naphthenic acid sodium and little molecular naphthenic acid sodium.Backwash liquor passes through H
+saturated MSC H Form H type cation exchange resin column, is replaced into naphthenic acid by naphthenic acid sodium salt.Part by H type cation exchange resin column is little molecular naphthenic acid, and the part being deposited on H type cation exchange resin column is large molecular naphthenic acid.Alkali lye (as the 1mol/L NaOH) backwash of 2～5 times of H type cation exchange resin bed layer volumes for H type cation exchange resin column, adjusts backwash liquor pH≤2 with HCl, and at 0～5 ℃ of standing 24h, to precipitate large molecular naphthenic acid.Large molecular naphthenic acid precipitates filtration successively, washed with de-ionized water, centrifugal, finally uses freeze dryer freeze-drying, obtains large molecular naphthenic acid solid sample.Solution by adsorption resin column is concentrated into 100～200mL with Rotary Evaporators, then uses freeze dryer freeze-drying, obtains little molecular solid sample.
The enrichment times of the inventive method naphthenic acid and the recovery are all higher, can from 0.5～50L wastewater sample, extract naphthenic acid, the naphthenic acid recovery is not less than 85%, the purity of preparing naphthenic acid is good, preparation amount meets the needs of naphthenic acid comprehensive characterization completely, be applicable to the enrichment of naphthenic acid in all kinds of oil refining or oil field waste, separation and sample preparation, the electro-desalting waste water that is particularly useful for refinery processing highly acid crude oil, produce the oil field extracted water of high-acid crude oil, extraction and preparation containing naphthenic acid in alkali polymer flooding water and oil-sand extraction pitch technique waste water, the sample of preparation can be used for naphthenic acid content, molecular weight distribution or structural characterization.
Accompanying drawing explanation
Fig. 1 is the inventive method operating process FB(flow block).
Embodiment
Embodiment 1
Amberlite DAX-8 resin (SUPELCO) soaks 24h with 0.1mol/L NaOH, then uses washed with de-ionized water, to remove remaining NaOH.Resin after cleaning extracts 16h by each Soxhlet of methylene chloride, acetone and methyl alcohol successively.800mL DAX-8 resin after purifying is packed in the glass column of long 700mm internal diameter 40mm, and the two ends of glass column are fixed with glass wool.Next use successively deionized water, 0.1mol/LNaOH, deionized water, 0.1mol/L HCl and washed with de-ionized water, until the total organic carbon of eluent (TOC) is lower than 1.0mg/L.
MSC H Form Zeo-karb extracts after 16h by methyl alcohol Soxhlet, is stored in methyl alcohol.MSC H Form Zeo-karb after about 800mL purifies packs in the glass column with the same specification of DAX-8 resin column.Resin column is used deionized water, 0.1mol/L NaOH, deionized water, 0.1mol/L HCl and washed with de-ionized water successively, until the TOC of eluent is lower than 0.5mg/L.Now MSC H Form cation exchange resin column is H
+saturation type.
The standing 24h of certain desalting in oil refinery biochemical treatment water outlet, fully, after settling suspension thing, gets upper strata clear water 10L, with HCl, adjusts pH=2, then with 25mL/min, passes through DAX-8 resin column, measures the TOC of effluent.Resin column after absorption is washed remaining sample off with deionized water, next uses 5L 0.1mol/L NaOH backwash, measures the TOC of backwash liquor.The organism that backwash is got off is naphthenic acid, comprises large molecule and little molecular naphthenic acid.Backwash liquor is by MSC H type cation exchange resin column, by Na
+be replaced into H
+.Part by resin column is little molecular naphthenic acid, and the part being deposited on resin column is large molecular naphthenic acid.The 1mol/L NaOH backwash of 2.0L for resin column, adjusts backwash liquor pH≤2, and stores 24h at 5 ℃, to precipitate large molecular naphthenic acid.Sediment filtration successively, washed with de-ionized water, centrifugal, finally use the desk-top freeze-drying system freeze-drying of Labconco FreeZone 4.5-Liter, obtains large molecular naphthenic acid solid sample 42mg.Solution by MSC-1H cation exchange resin column is concentrated into 150mL with Buchi R-144 Rotary Evaporators, then uses the desk-top freeze-drying system freeze-drying of Labconco FreeZone 4.5-Liter, obtains little molecular solid sample 380mg.In this desalting in oil refinery bio-chemical effluent, the content of large molecular naphthenic acid and little molecular naphthenic acid is respectively 4.2mg/L and 38.0mg/L.
The naphthenic acid recovery is 87.2% as calculated.
Embodiment 2
The standing 24h of certain desalting in oil refinery biochemical treatment water outlet, fully, after settling suspension thing, gets upper strata clear water 15L, by the separation of embodiment 1 and preprocessor, prepares large molecular naphthenic acid solid sample 63mg and little molecular solid sample 462mg.In this desalting in oil refinery bio-chemical effluent, the content of large molecular naphthenic acid and little molecular naphthenic acid is respectively 4.2mg/L and 40.8mg/L.
Embodiment 3
The standing 24h of certain polymer flooding water of oil field biochemical treatment water outlet, fully, after settling suspension thing, gets upper strata clear water 20L, by the separation of embodiment 1 and preprocessor, prepares large molecular naphthenic acid solid sample 84mg and little molecular solid sample 336mg.In this polymer flooding water of oil field biochemical treatment water outlet, the content of large molecular naphthenic acid and little molecular naphthenic acid is respectively 4.2mg/L and 16.8mg/L.
Claims (7)
1. a preparation method for naphthenic acid sample in wastewater, process is as follows:
(1) wastewater sample is adjusted to after acidity, by adsorption resin column, adsorbs acidity and Neutral Organic Compound wherein, and polymeric adsorbent is styrene-divinylbenzene polymer resin;
(2) the adsorption resin column alkali lye backwash after absorption, obtains the first backwash liquor, with the acid organism of wash-out;
(3) described the first backwash liquor is by H type cation exchange resin column, and the solution by H type cation exchange resin column, through rotary evaporation and freeze-drying, obtains little molecular naphthenic acid solid sample;
(4) the sediment alkali lye backwash on H type cation exchange resin column, obtain the second backwash liquor, described the second backwash liquor is less than or equal to 2 with hydrochloric acid adjust pH, standing and collecting precipitation thing, sediment after filtration, after cleaning, centrifugal, freeze-drying, obtain large molecular naphthenic acid solid sample;
Measure respectively the quality of little molecular naphthenic acid solid sample and large molecular naphthenic acid solid sample and determine its content in waste water;
The little molecular naphthenic acid solid sample of preparation or large molecular naphthenic acid ultimate analysis for solid sample, solid-state 13C nuclear magnetic resonance method, Fourier transform infrared spectrometry and atmospheric pressure ionization mass spectroscopy characterize molecular weight and the architectural feature of naphthenic acid;
Described large molecular naphthenic acid is water insoluble under acid condition, i.e. insoluble naphthenic acid; Little molecular naphthenic acid is all water-soluble under any pH, i.e. solubility naphthenic acid.
2. it is characterized in that in accordance with the method for claim 1: polymeric adsorbent and H type Zeo-karb carry out purified treatment before filling.
3. it is characterized in that in accordance with the method for claim 1: step (1) wastewater sample is adjusted to acid pH≤2.
4. it is characterized in that in accordance with the method for claim 1: the alkali lye backwash process of the adsorption resin column after step (2) absorption is for to carry out backwash with the alkali lye of 5～8 times of polymeric adsorbent bed volume.
5. in accordance with the method for claim 1, it is characterized in that: described the first backwash liquor of step (3) is by after H type cation exchange resin column, solution freeze-drying after rotary evaporation 100～200mL by H type cation exchange resin column, obtains little molecular naphthenic acid solid sample.
6. it is characterized in that in accordance with the method for claim 1: the alkali lye backwash of 2～5 times of H type cation exchange resin bed layer volumes for the sediment on step (4) H type cation exchange resin column.
7. it is characterized in that in accordance with the method for claim 1: wastewater sample consumption is 0.5～50L.
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| CN107935232A (en) * | 2017-11-01 | 2018-04-20 | 中国石油天然气集团公司 | A kind of electro-desalting is given up the separation method of Organic substance in water |
| CN110208412A (en) * | 2019-06-18 | 2019-09-06 | 青岛科技大学 | A kind of coal chemical industrial waste water key intoxicating object knowledge method for distinguishing |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1205985A (en) * | 1997-07-22 | 1999-01-27 | 中国石油化工总公司 | Treatment process of naphthenic acid effluents in oil refinery |
| US5922206A (en) * | 1997-09-15 | 1999-07-13 | Amcol International Corporation | Process for treating water for removal of oil and water-soluble petroleum oil components |
| EP1840567A1 (en) * | 2006-03-30 | 2007-10-03 | Oil Plus Limited | Crude oil screening process |
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- 2010-07-07 CN CN201010222011.6A patent/CN102313658B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1205985A (en) * | 1997-07-22 | 1999-01-27 | 中国石油化工总公司 | Treatment process of naphthenic acid effluents in oil refinery |
| US5922206A (en) * | 1997-09-15 | 1999-07-13 | Amcol International Corporation | Process for treating water for removal of oil and water-soluble petroleum oil components |
| EP1840567A1 (en) * | 2006-03-30 | 2007-10-03 | Oil Plus Limited | Crude oil screening process |
Non-Patent Citations (4)
| Title |
|---|
| 孔令照 等.柴油脱除环烷酸精制工艺研究进展.《石油化工高等学校学报》.2004,第17卷(第3期),37-41. |
| 李凌波 等.炼油厂达标废水中溶解性有机物的表征.《环境科学学报》.2004,第24卷(第2期),265-270. |
| 柴油脱除环烷酸精制工艺研究进展;孔令照 等;《石油化工高等学校学报》;20040930;第17卷(第3期);37-41 * |
| 炼油厂达标废水中溶解性有机物的表征;李凌波 等;《环境科学学报》;20040331;第24卷(第2期);265-270 * |
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