CN103675155B - Headspace light dydrocarbon sample preservation system and method - Google Patents
Headspace light dydrocarbon sample preservation system and method Download PDFInfo
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- CN103675155B CN103675155B CN201210342517.XA CN201210342517A CN103675155B CN 103675155 B CN103675155 B CN 103675155B CN 201210342517 A CN201210342517 A CN 201210342517A CN 103675155 B CN103675155 B CN 103675155B
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Abstract
The invention provides a headspace light dydrocarbon sample preservation system and a headspace light dydrocarbon sample preservation method. The system comprises a container for preserving a sample to be detected, wherein gas/liquid-phase equilibrium liquid which accounts for 70-85 volume percent is contained in the container; a bottle opening of the container is sealed; the gas/liquid-phase equilibrium liquid is a saturated sodium chloride solution containing 2-bromoethane sulfonate; the concentration of the 2-bromoethane sulfonate in the gas/liquid-phase equilibrium liquid is 20-200mM. The method comprises the following steps: filling the sample to be detected into the container; adding the gas/liquid-phase equilibrium liquid in the amount into the container, sealing and inverting the container until gas, liquid (solid) phases are balanced, so that the sample to be detected can be preserved for a long time. According to the system and the method, the methanogenic activity can be effectively inhibited, the biological methane gas interference caused by long transportation and preservation time is eliminated, the specificity and reliability of oil and gas chemical exploration are improved, and the system is suitable for large-scale industrial exploration measurement with multiple samples.
Description
Technical field
The present invention relates to a kind of head space lighter hydrocarbons Sample storage system for hydrocarbon geochemical exploration field, say further, relate to a kind of head space lighter hydrocarbons Sample storage system and method.
Background technology
Hydrocarbon geochemical exploration is the Geochemical Exploration Methods mainly finding object with oil and natural gas.The impact of the vestige that primary oil gas carries in migration and accumulation process and production, make the component in the media such as the soil of surrounding, rock and underground water that significant change occur, cause local geochemical anomaly, become the information of look for oil and gas, this is the foundation of hydrocarbon geochemical exploration.Hydrocarbon geochemical exploration is a kind of comprehensive measuring method of multi objective, and wherein head space lighter hydrocarbons (static headspace gas) are hydrocarbon geochemical exploration very important indexs.
The old process that head space lighter hydrocarbons detect is: measure the content of these components in raw sample by the gas componant above sample substrate, the container containing saturated aqueous common salt is loaded fast by institute's sample thief, the head space lighter hydrocarbons in sample are made to be issued to sorption and desorption balance in the condition of correspondence, according to Raoult's law, when gas, liquid (Gu) balance each other time, the vapor pressure of each component to its liquid (Gu) mutually in concentration and saturated vapour pressure be directly proportional.Lighter hydrocarbons and other volatile components vapor pressures are large, concentration in the gas phase much larger than liquid (Gu) mutually in concentration.Therefore, without any separating treatment, directly can extract headspace gas inject gas chromatograph and measure, analyze the content of wherein each light hydrocarbon component in airtight container.This wherein, because methane gas in the lighter hydrocarbons that float from hydrocarbon-bearing pool has comparative advantage, therefore the abnormal of head space methane gas all has good indicative function to oil reservoir and gas reservoir.
But because some is high containing organic pedotheque, as rice terrace, lake bed sediment, marsh sample etc., in long preservation transportation, be easy to cause anaerobism or local anaerobic state, even if under the condition of high salt, also can create good life condition to methanogen, thus produce methane gas, finally affect the accuracy of hydrocarbon geochemical exploration.Although Carbon isotope technology can judge the source of methane in soil effectively by the Carbon Isotope Characteristics of methane, but for biogenesis natural gas pool, derive from the methane blended that in the lighter methane of the carbon isotope of gas reservoir and surface soil, carbon isotope is heavier, the Methane Carbon Isotope in soil can be caused to form change a lot, cause the phenomenon of the Methane Carbon Isotope substantial deviation in the pedotheque Methane Carbon Isotope value of actual measurement and hydrocarbon-bearing pool.In addition, once give birth to methane gas after transport and storage stage create, be irreversible on the impact that subsequent quantitation detects and abnormality juding causes.It is pointed out that except head space lighter hydrocarbons, the activity light hydrocarbon index such as dissolved hydrocarbon also can by the interference of rear raw methane gas.
Given this, a kind of head space lighter hydrocarbons store method that can suppress methanogenesis activity of necessary exploitation, to avoid rear raw methane gas to affect test result, improves specificity and the reliability of hydrocarbon geochemical exploration.
Summary of the invention
In order to overcome the deficiencies in the prior art, the present invention is devoted to provide a kind of head space lighter hydrocarbons Sample storage system and method.
A kind of head space lighter hydrocarbons Sample storage system and method for the present invention, head space lighter hydrocarbons detection specificity can be improved with methane phase inhibitor, visit head space lighter hydrocarbons in conventional gas and oilization to detect on basis, by adding specificity methane phase inhibitor in container, effectively to suppress methanogenesis activity, thus eliminate the interference of biomethanation gas, improve specificity and the reliability of hydrocarbon geochemical exploration detection.One of the object of the invention is to provide a kind of head space lighter hydrocarbons Sample storage system, and this system comprises the container preserving testing sample.Splendid attire gas-liquid phase equilibrium liquid in described container, container finish is with sealing.
In order to ensure there being certain headroom, the volume that wherein gas-liquid phase equilibrium liquid accounts for container is not more than 85%, and preferably accounting for described vessel volume is 75 ~ 85%.
2-bromoethane sulfonic acid salt (BES) is the analogue of coenzyme M specific to methanogen, optionally suppress all methanogens, and other microorganisms is unaffected.
In order to realize the generation suppressing methane, gas-liquid equilibrium liquid described in saved system of the present invention is saturated sodium-chloride (NaCl) solution containing 2-bromoethane sulfonic acid salt.Wherein, the concentration in gas-liquid phase equilibrium liquid of described 2-bromoethane sulfonic acid salt is that 20-200mM(concentration unit mM refers to per mille mole often liter, also can be expressed as mmol/L), preferred 40-70mM, more preferably 50mM.
The saturation concentration of saturated nacl aqueous solution used in the present invention, refers to the saturation concentration of salt at normal temperatures.At general 20 DEG C, the solubleness of sodium chloride in 100g water is 36g.
The present invention selects the reason of the saturated aqueous solution of Nacl: in theory according to Henry's law, and other saturated salt solutions also can reduce the solubleness of gas in equilibrium liquid, and the gas in soil is discharged in headroom effectively.But static headspace gas detects general employing NaCl aqueous solution, and reason one NaCl aqueous solution can suppress the microbial activity in soil to avoid it to discharge gas, interference detection results; Reason two is convenient to work area purchase in the wild, is used while allocating.And why must be saturated solution, be according to Henry's law, saturated salt solution can reduce the solubleness of gas in equilibrium liquid, and the gas in soil is discharged in headroom effectively.
The described sealing for airtight container bottleneck can for any not with the salable gas of test sample and this area routine of reacting of vapor liquid equilibrium liquid, liquid (Gu) packoff of body, as adopted the double-layer sealing structure of common sealed membrane, rubber plug and bottle cap.Preferred rubber plug and bottle cap double-layer sealing structure, wherein rubber plug fills in bottleneck, and bottle cap plays the effect of fixing rubber plug, if air pressure increases in bottle, rubber plug can be avoided to loosen, to keep the sealing of system.The screw top closure of the optional plastics of bottle cap or metal.Be corresponding helicitic texture between container finish outer wall with screw top closure inwall, screw top closure is tightened in outside container finish.If bottle cap is selected from crown cap, then Manual cap pressing machine mode also can be adopted directly to be pressed by bottle cap to wrap in and be plugged with outside the bottleneck of rubber plug, play fixing and sealing function.The wherein double-decker of preferred rubber plug and screw top closure.More preferably, described rubber plug is polyisobutyl rubber plug; Screw top closure is aluminium lid.
Described container can be selected from various plastics in prior art or glass, can the container of carrying liquid.Such as serum bottle, conical flask, glass infusion bottle etc.But preferably adopt the container of glass material to guarantee impermeability.Gas is got with the later stage, preferred serum bottle in order to field is convenient for carrying; With reference to petroleum industry standard SY/T 6009.3-2003 hydrocarbon geochemical exploration Specimen Determination method, be more preferably the serum bottle that volume is 250ml, so that compare the sample result of different batches.
Two of object of the present invention is to provide a kind of head space lighter hydrocarbons sample preservation, is specially:
Described testing sample is loaded in described container, then adds described gas-liquid phase equilibrium liquid to vessel volume between 70 ~ 85%, the preferably position of 75 ~ 85%, immediately airtight container bottleneck, preserve after being inverted.In order to reach fully gas, liquid (Gu) balance each other, general to be inverted at least 10 minutes.
Wherein said testing sample is the various measuring media needing to carry out the measurement of head space lighter hydrocarbons in this area.Generally being selected from soil, landwaste or mean grain size is at least one in the rock core of below 0.5cm.
Most preferably, load after soil or landwaste (mud flush is clean) or rock core (breaking into pieces to below particle diameter 0.5cm) sampling rapidly in 250mL container, add saturated Nacl salt solution containing 2-bromoethane sulfonic acid salt (final concentration 50mM) to upper vessel portion remaining space 50mL, immediately with the sealing of isobutyl plug, be inverted within least 10 minutes, reach gas, liquid (Gu) balance each other, can preserve to be measured for a long time.Utilize the method effectively can suppress methanogenesis activity, eliminate the biological methane gas interference caused due to longer transport and holding time.
Head space lighter hydrocarbons sample preservation can be transported to laboratory and directly extract headspace gas inject gas chromatograph or through the freezing enrichment of pre-column, then thermal desorption enters gas chromatograph for determination by head space lighter hydrocarbons Sample storage system of the present invention.
The present invention preserves in the container of gas and adds certain density methane phase inhibitor in conventional sense, suppresses the generation of biological methane gas, thus meets 3 conditions: (1) suppresses various methanogen and activity thereof specifically; (2) other microorganisms are not affected; (3) medicine itself does not produce escaping gas, does not also adsorb or absorption of light hydrocarbon gas.
Feature of the present invention: the present invention is the system and method set up for improving static headspace gas detection specificity.Effectively can suppress methanogenesis activity by adding specificity methane phase inhibitor in container, preserving head space lighter hydrocarbons sample better, eliminating the interference that biological methane gas measures head space lighter hydrocarbons.Its feature is: (1) operating process is simple, and economical and practical, inhibition is good; (2) suppress various methanogen and activity thereof using 2-bromoethane sulfonic acid salt specifically as inhibitor, do not affect other microbial populations again simultaneously; (3) medicine itself does not produce escaping gas, does not also adsorb or absorption of light hydrocarbon gas; (4) also can use in the test of dissolved hydrocarbon, detection specificity can be made to increase, detect data more reliable.
Accompanying drawing explanation
Fig. 1 is the schematic diagram of head space lighter hydrocarbons Sample storage system of the present invention.
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Head space lighter hydrocarbons Sample storage system of the present invention is made up of serum bottle 1, isobutyl plug 2, spiral aluminum bottle cap 3, gas-liquid phase equilibrium liquid 4 as shown in Figure 1.Be head space lighter hydrocarbons 5(static headspace gas on gas-liquid phase equilibrium liquid), account for serum bottle volume.Described gas-liquid phase equilibrium liquid is the saturated NaCl solution (saturated solution concentration expressed in percentage by weight is 26.5%wt) containing 50mM 2-bromoethane sulfonic acid salt.
Concrete operation steps is: load 250mL serum bottle 1 rapidly by after the testing sample sampling one of at least of soil, landwaste (mud flush is clean), rock core (breaking into pieces to below particle diameter 0.5cm), add described gas-liquid phase equilibrium liquid 200ml, seal with isobutyl plug 2 and spiral aluminum bottle cap 3 immediately, be inverted within 10 minutes, reach gas, liquid (Gu) balance each other after, preservation is transported to laboratory and directly extracts headspace gas head space lighter hydrocarbons (static headspace gas) 5 inject gas chromatograph or through the freezing enrichment of pre-column, then thermal desorption enters gas chromatograph for determination.
Corresponding, conventional head space methane gas saved system and method: load 250mL glass infusion bottle rapidly by after testing sample sampling, add saturated Nacl salt solution to upper vessel portion remaining space 50mL, seal with isobutyl plug, be inverted within 10 minutes, reach gas, liquid (Gu) balance each other, be transported to laboratory and directly extract headspace gas head space lighter hydrocarbons (static headspace gas) inject gas chromatograph or through the freezing enrichment of pre-column, then thermal desorption enters gas chromatograph for determination.But the biological methane gas interference that general longer transport and holding time often cause.
Head space lighter hydrocarbons Sample storage system and method for the present invention and described conventional head space methane gas saved system and method is used to carry out Collection and conservation to the head space methane gas (i.e. sample 1 and sample 2) of two rice terrace samples respectively, after the storage life of 1 month, the sample of preservation is carried out follow-up head space concentration of methane gas and measured.Its measurement result is in table 1.
Table 1
As shown in table 1, to the water paddy soil sample of two separate sources, adopt the present invention and conventional head space methane gas detection system to detect respectively.After the storage life of 1 month, system and method of the present invention restrained effectively biomethanation activity, the head space concentration of methane gas of paddy soil sample decreases 95% and 42% respectively than conventional method, eliminate the interference of biological methane gas to the full extent, thus improve specificity and the reliability of hydrocarbon geochemical exploration detection.
Restrained effectively methanogenesis activity after adopting system and method for the present invention, eliminate the interference of biological methane gas, improve specificity and the reliability of hydrocarbon geochemical exploration detection, have broad application prospects.
Claims (9)
1. a head space lighter hydrocarbons Sample storage system, comprises the container preserving testing sample, it is characterized in that:
Be loaded with the gas-liquid phase equilibrium liquid accounting for its volume 70% ~ 85% in described container, container finish is with sealing; Described gas-liquid phase equilibrium liquid is the saturated nacl aqueous solution containing 2-bromoethane sulfonic acid salt; Wherein, the concentration of 2-bromoethane sulfonic acid salt in described gas-liquid phase equilibrium liquid is 20-200mmol/L.
2. head space lighter hydrocarbons Sample storage system as claimed in claim 1, is characterized in that:
Wherein the concentration of 2-bromoethane sulfonic acid salt in described gas-liquid phase equilibrium liquid is 40-70mmol/L.
3. head space lighter hydrocarbons Sample storage system as claimed in claim 1, is characterized in that:
It is 75 ~ 85% that described gas-liquid phase equilibrium liquid accounts for vessel volume.
4. head space lighter hydrocarbons Sample storage system as claimed in claim 1, is characterized in that:
The sealing of described container finish comprises the double-decker of rubber plug and screw top closure; Wherein, rubber plug fills in bottleneck; Be corresponding helicitic texture between container finish outer wall with screw top closure inwall, screw top closure is tightened in outside container finish; Described screw top closure is metal or plastic material.
5. head space lighter hydrocarbons Sample storage system as claimed in claim 1, is characterized in that:
Described rubber plug is polyisobutyl rubber plug; Screw top closure is aluminium lid.
6. head space lighter hydrocarbons Sample storage system as claimed in claim 1, is characterized in that:
One in described selection of container serum bottle, conical flask, glass infusion bottle; Container material quality is selected from plastics or glass.
7. adopt the method for carrying out head space lighter hydrocarbons Sample storage of the saved system as described in one of claim 1 ~ 6, it is characterized in that:
Described testing sample is loaded in described container, then adds the gas-liquid phase equilibrium liquid of described amount, airtight container bottleneck immediately, be inverted.
8. the method for head space lighter hydrocarbons Sample storage as claimed in claim 7, is characterized in that:
It is at least one in the rock core of below 0.5cm that described testing sample is selected from soil, landwaste or mean grain size.
9. the method for head space lighter hydrocarbons Sample storage as claimed in claim 7, is characterized in that:
Described testing sample is loaded in container, then adds the gas-liquid phase equilibrium liquid of described amount, seal bottleneck immediately, be inverted at least 10 minutes.
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| CN107192786B (en) * | 2017-07-04 | 2018-05-11 | 国家地质实验测试中心 | The enrichment preparation facilities and its method of gas in a kind of water body |
| CN108020608A (en) * | 2017-11-19 | 2018-05-11 | 桂林理工大学 | A kind of method of methane content in detection water |
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