CN107796861B - Method for detecting content of organic chlorine in crude oil containing free water - Google Patents
Method for detecting content of organic chlorine in crude oil containing free water Download PDFInfo
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- CN107796861B CN107796861B CN201610802241.7A CN201610802241A CN107796861B CN 107796861 B CN107796861 B CN 107796861B CN 201610802241 A CN201610802241 A CN 201610802241A CN 107796861 B CN107796861 B CN 107796861B
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
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- C10G7/04—Dewatering
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Abstract
The invention discloses a method for detecting the content of organic chlorine in crude oil containing free water, which comprises the following steps: performing primary oil-water separation, and measuring the viscosity at 60 ℃; when the viscosity is less than 300mPa.s, hermetically dehydrating for 2h at 60 ℃, and measuring the content of organic chlorine in the product by using a micro-coulomb method; when the viscosity is more than 300mPa.s, adding 120# solvent oil into the crude oil, and removing water by adopting a distillation reflux mode; reading the dewatering volume; transferring the distilled 120# solvent oil back to the crude oil, putting the crude oil into a distillation instrument, and measuring the content of organic chlorine in the crude oil by a micro-coulomb method; and substituting the recording related data into a formula for calculation. According to the method, the crude oil containing the free water is divided into low-density crude oil and low-viscosity crude oil and high-density crude oil and high-viscosity crude oil according to the viscosity and the density, the difficult problem in the aspect of detecting the organochlorine of the crude oil containing the free water is solved by adopting different dehydration and determination modes, when the organochlorine scalar exceeds 3ug/g, the detection result is high in credibility, and the relative error is within 10%.
Description
Technical Field
The invention relates to a method for detecting the content of organic chlorine in crude oil containing free water.
Background
At present, the domestic detection method for the content of organic chlorine in crude oil is GB/T18612-2011 microcoulomb method for determining the content of organic chlorine in crude oil, the method determines the content of organic chlorine in crude oil by determining the content of organic chlorine in distillate oil before 204 ℃ in the crude oil, the method is suitable for determining dehydrated export purified crude oil, and wellhead crude oil containing free water is not suitable for detecting the content of organic chlorine in the crude oil containing free water because the wellhead crude oil has high water content and difficult dehydration and cannot be directly distilled. In order to enhance the source control of crude oil organochlorine and the tracing of organochlorine pollution sources in oil field enterprises, a method for determining the organochlorine content in crude oil containing free water needs to be established.
Disclosure of Invention
Aiming at the prior art, the invention provides a method for detecting the content of organic chlorine in crude oil containing free water. The invention improves the existing crude oil organochlorine content detection method, divides the crude oil containing free water into low-density and low-viscosity crude oil and high-density and high-viscosity crude oil according to the viscosity and the density, and solves the problem of organochlorine detection of the crude oil containing free water by adopting different dehydration and determination modes.
The invention is realized by the following technical scheme:
a method for detecting the content of organic chlorine in crude oil containing free water comprises the following steps:
(1) placing crude oil to be detected containing free water in a constant-temperature water bath at 60-80 ℃ for 30min to primarily separate oil from water;
(2) taking out the crude oil containing emulsified water in the upper layer, and measuring the viscosity of the crude oil at 60 ℃;
(3) according to the determination result, when the viscosity is less than 300mPa.s, an electric dessicator is used for hermetically dehydrating at 60 ℃ for 2h, then a fraction before 320 ℃ is obtained by distillation, and the content of organic chlorine in the fraction is determined by a microcurrent method;
(4) according to the measurement result of the step (2), when the viscosity is more than 300mPa.s, adding 120# solvent oil (the mass ratio of the crude oil to the solvent oil is 4.5-5.5: 1, preferably 5:1) into the crude oil, and removing water by adopting a distillation reflux mode (as shown in figure 1, a conventional technical means);
(5) after the dehydration is finished, reading the dehydration volume, transferring the distilled 120# solvent oil back to the crude oil (the added solvent oil has the function of assisting the dehydration, and the dehydrated solvent oil cannot be separated from the crude oil, so that the influence of the introduced solvent oil on the final result needs to be quantified), and uniformly mixing;
(6) putting the dehydrated crude oil obtained in the step (5) and the solvent oil returned into a distillation apparatus, obtaining fractions before 320 ℃, and measuring the content of organic chlorine in the fractions by a micro-coulomb method; meanwhile, a 120# solvent oil organochlorine blank experiment (measuring the organochlorine content of 120# solvent oil) is carried out, and the recording related data are substituted into the following formula for calculation:
in the formula:
w' -crude oil organochlorine content, mg/kg;
m3-mass of crude oil containing free water, g, before dehydration;
m4-mass of added 120# mineral spirits, g;
m5-total mass of dehydrated water, g;
m6-crude oil mass after distillation dehydration, g;
delta m-320 ℃ front distillate quality, g;
ρ3-320 ℃ front distillate density, g/cm 3;
ρ4-120 # solvent oil density, g/cm 3;
c3the organic chlorine content of the front cut oil at the temperature of 320 ℃ is mu g/mL;
c4120# solvent oil organic chlorine content,. mu.g/mL.
The method for detecting the content of the organic chlorine in the crude oil containing the free water has the density of less than 925kg/m3And the viscosity of the crude oil containing water at 60 ℃ is less than 300mPa.s, the crude oil is dehydrated by adopting a closed electric dehydration instrument, the water in the crude oil can be effectively removed, the operation is simple, and the determination of the content of the organic chlorine cannot be influenced after dehydration.
For a density greater than 925kg/m3And the crude oil with the viscosity of more than 300mPa.s at 60 ℃ is dehydrated by adding the 120# solvent oil in an auxiliary distillation mode (by utilizing the characteristic of azeotropy of the 120# solvent oil and water), so that the carrying amount of water vapor is increased, and the distillation dehydration efficiency is improved.
The method for detecting the content of the organic chloride in the crude oil containing the free water realizes the detection of the content of the organic chloride in the crude oil containing the free water, and when the organic chloride scalar exceeds 3ug/g, the detection result has high credibility and the relative error is within 10 percent. The experimental equipment and appliances used by the invention are relatively simple, and are easy to realize large-scale popularization and convenient for use by basic units.
Drawings
FIG. 1: schematic diagram of distillation dehydration equipment.
Wherein, 1, a condenser pipe; 2. connecting with a low-temperature water bath; 3. a receiver; 4. a valve; 5. a measuring cylinder; 6. distilling the flask; 7. an electric heating jacket.
Detailed Description
The present invention will be further described with reference to the following examples.
The instruments, reagents, materials and the like used in the following examples are conventional instruments, reagents, materials and the like in the prior art and are commercially available in a normal manner unless otherwise specified. Unless otherwise specified, the experimental methods, detection methods, and the like described in the following examples are conventional experimental methods, detection methods, and the like in the prior art.
EXAMPLE 1 detection of organochlorine content in crude oil containing free Water
The method comprises the following steps:
(1) placing crude oil to be detected containing free water in a constant-temperature water bath at 60-80 ℃ for 30min to primarily separate oil from water;
(2) taking out the crude oil containing emulsified water in the upper layer, and measuring the viscosity of the crude oil at 60 ℃;
(3) according to the determination result, when the viscosity is less than 300mPa.s, an electric dessicator is used for hermetically dehydrating at 60 ℃ for 2h, then a fraction before 320 ℃ is obtained by distillation, and the content of organic chlorine in the fraction is determined by a microcurrent method;
(4) according to the determination result of the step (2), when the viscosity is more than 300mPa.s, adding 120# solvent oil (the mass ratio of the crude oil to the solvent oil is 5:1) into the crude oil, and removing water by adopting a distillation reflux mode;
(5) after the dehydration is finished, reading the dehydration volume, transferring the distilled 120# solvent oil back to the crude oil, and uniformly mixing;
(6) putting the dehydrated crude oil obtained in the step (5) and the solvent oil returned into a distillation apparatus, obtaining fractions before 320 ℃, and measuring the content of organic chlorine in the fractions by a micro-coulomb method; meanwhile, a 120# solvent oil organochlorine blank experiment (measuring the organochlorine content of 120# solvent oil) is carried out, and the recording related data are substituted into the following formula for calculation:
in the formula:
w' -crude oil organochlorine content, mg/kg;
m3-mass of crude oil containing free water, g, before dehydration;
m4-mass of added 120# mineral spirits, g;
m5-total mass of dehydrated water, g;
m6-crude oil mass after distillation dehydration, g;
delta m-320 ℃ front distillate quality, g;
ρ3-320 ℃ front distillate density, g/cm 3;
ρ4-120 # solvent oil density, g/cm 3;
c3the organic chlorine content of the front cut oil at the temperature of 320 ℃ is mu g/mL;
c4120# solvent oil organic chlorine content,. mu.g/mL.
The results of the actual test conducted by the above method are shown in Table 1.
TABLE 1 results of organochlorine measurement of spiked crude oils
Tests show that the extraction, distillation and dehydration method can effectively remove water from crude oil containing about 40% of emulsified water, and when the amount of the added organic chlorine exceeds 3ug/g, the measured value of the organic chlorine content of the dehydrated crude oil has high credibility, and the relative error of the method is within 10%.
Although the specific embodiments of the present invention have been described with reference to the examples, the scope of the present invention is not limited thereto, and those skilled in the art will appreciate that various modifications and variations can be made without inventive effort by those skilled in the art based on the technical solution of the present invention.
Claims (2)
1. A method for detecting the content of organic chlorine in crude oil containing free water is characterized by comprising the following steps: the method comprises the following steps:
(1) placing crude oil to be detected containing free water in a constant-temperature water bath at 60-80 ℃ for 30min to primarily separate oil from water;
(2) taking out the crude oil containing emulsified water at the upper layer in the step (1), and measuring the viscosity of the crude oil at 60 ℃;
(3) according to the determination result of the step (2), when the viscosity is less than 300mPa.s, using an electrodeionization instrument, hermetically dehydrating at 60 ℃ for 2h, then obtaining a fraction before 320 ℃ by distillation, and determining the content of organic chlorine by using a microcurrent method;
(4) according to the determination result of the step (2), when the viscosity is more than 300mPa.s, adding 120# solvent oil into the crude oil, wherein the mass ratio of the crude oil to the solvent oil is 4.5-5.5: 1, and dehydrating in a distillation reflux manner;
(5) after the dehydration in the step (4) is finished, reading the dehydration volume, transferring the distilled 120# solvent oil back to the crude oil, and uniformly mixing;
(6) placing the dehydrated crude oil obtained in the step (5) and converted from the solvent oil into a distillation apparatus, obtaining fractions before 320 ℃, and determining the content of organic chlorine in the fractions by a micro-coulomb method; meanwhile, a blank experiment of organochlorine in No. 120 solvent oil is carried out, the organochlorine content in No. 120 solvent oil is measured, and relevant data are recorded and substituted into the following formula for calculation:
in the formula:
w' -the content of organic chlorine of crude oil containing free water, mg/kg;
m3-mass of crude oil containing free water, g, before dehydration;
m4-mass of added 120# mineral spirits, g;
m5-total mass of dehydrated water, g;
m6-crude oil mass after distillation dehydration, g;
delta m-320 ℃ front distillate quality, g;
ρ3-320 ℃ front distillate density, g/cm 3;
ρ4-120 # solvent oil density, g/cm 3;
c3the organic chlorine content of the front cut oil at the temperature of 320 ℃ is mu g/mL;
c4120# solvent oil organic chlorine content,. mu.g/mL.
2. The method of claim 1 for detecting the organochlorine content of crude oil containing free water, wherein the method comprises the following steps: in the step (4), the mass ratio of the crude oil to the solvent oil is 5: 1.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1585305A (en) * | 1976-12-06 | 1981-02-25 | Texaco Development Corp | Detection of impurities in fluid flowing in refinery pipeline or oil production operations using nuclear techniques |
| CN204758598U (en) * | 2015-07-24 | 2015-11-11 | 山东德丰石油装备有限公司 | Organic chlorine of crude oil test distillation appearance |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1585305A (en) * | 1976-12-06 | 1981-02-25 | Texaco Development Corp | Detection of impurities in fluid flowing in refinery pipeline or oil production operations using nuclear techniques |
| CN204758598U (en) * | 2015-07-24 | 2015-11-11 | 山东德丰石油装备有限公司 | Organic chlorine of crude oil test distillation appearance |
Non-Patent Citations (3)
| Title |
|---|
| Distribution and Identification of Chlorides in Distillates from YS Crude Oil;Bencheng Wu et.al;《Energy Fuels》;20150210;第29卷;第1391-1396页 * |
| 原油/馏分油中氯的分布规律;樊秀菊 等;《辽宁石油化工大学学报》;20091215;第29卷(第4期);第39-42页 * |
| 油田化学剂中有机氯含量的测定;王丽娟 等;《精细石油化工进展》;20120425;第13卷(第4期);第47-50页 * |
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