# US 10,816,532 B2 · Methods and devices for detecting mercury isotopes in crude oil > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 10,816,532 B2 - Document ID: US10816532B2 - Status: Granted - Kind: B2 - Application number: 16/389,481 - Filed: 2019-04-19 - Published: 2020-04-30 - Granted: 2020-10-27 - Earliest claimed: 2018-10-31 - Assignees: PetroChina Company Limited - Applicants: PetroChina Company Limited - Inventors: Guangyou Zhu; Shunlin Tang - Web page: https://patentgrep.com/patent/US10816532B2 ## CPC - G01N 33/2835: {Specific substances contained in the oils or fuels} - G01N 21/3103: {Atomic absorption analysis} - G01N 21/6404: {Atomic fluorescence} - H01J 49/105: {using high-frequency excitation, e.g. microwave excitation, Inductively Coupled Plasma [ICP]} - G01N 2021/3107: {Cold vapor, e.g. determination of Hg} - G01N: INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES (measuring or testing apparatus or processes other than immunoassay, involving enzymes or microorganisms C12M, C12Q) - H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H) ## Abstract The present disclosure relates to a method and device for detecting mercury isotopes in crude oil. The device comprises an enrichment-absorption system and a secondary purification-enrichment system for mercury isotopes, wherein the enrichment-absorption system includes an air-background mercury absorption system, a pyrolysis/cracking system, a mercury-sample absorption system connected in series with pipe lines, and a vacuum pump, and the vacuum pump is connected to the mercury-sample absorption system through a pipe line; the secondary purification-enrichment system includes a nitrogen-gas cylinder, a collection bottle with potassium permanganate absorption liquid, and a secondary enrichment-absorption bottle connected in series with pipe lines, wherein the secondary purification-enrichment system further includes a stannous-chloride storage bottle, which is connected to a pipe line between the nitrogen-gas cylinder and the collection bottle with potassium-permanganate absorption liquid via a peristaltic pump and through a pipe line. ## Claims ### Claim 1 A device for detecting mercury isotopes in crude oil, which comprises an enrichment-absorption system and a secondary purification-enrichment system for mercury isotopes, wherein the enrichment-absorption system comprises an air-background mercury absorption system, a pyrolysis/cracking system, and a mercury-sample absorption system connected in series with pipe lines, and a vacuum pump, wherein the vacuum pump is connected to the mercury-sample absorption system through a pipe line; and the secondary purification-enrichment system comprises a nitrogen-gas cylinder, a collection bottle with potassium-permanganate absorption liquid, and a secondary enrichment-absorption bottle connected in series with pipe lines, wherein the secondary purification-enrichment system further comprises a stannous-chloride storage bottle, which is connected to a pipe line between the nitrogen-gas cylinder and the collection bottle with potassium-permanganate absorption liquid via a peristaltic pump and through a pipe line. ### Claim 2 (depends on 1) The device according to claim 1, wherein the air-background mercury absorption system comprises three impact samplers connected in series with pipe lines; the pyrolysis/cracking system comprises a pyrolysis chamber and a cracking chamber connected in series with pipe lines, wherein the pyrolysis chamber is connected via a pipe line to the last impact sampler in the connection order in the air-background mercury absorption system; and the mercury-sample absorption system comprises five impact samplers connected in series with pipe lines, wherein the first impact sampler in the connection order is connected via a pipe line to the cracking chamber of the pyrolysis/cracking system, and the vacuum pump is connected via a pipe line to the last impact sampler in the connection order of the mercury-sample absorption system. ### Claim 3 (depends on 2) The device according to claim 2, wherein the three impact samplers in the air-background mercury absorption system, in the connection order, are respectively a first impact sampler containing aqua regia, a second impact sampler containing aqua regia and a third impact sampler containing an aqueous sodium hydroxide solution, and the pyrolysis chamber is connected to the third impact sampler through a pipe line; and the five impact samplers in the mercury-sample absorption system, in the connection order, are respectively a fourth impact sampler containing a stannous chloride solution, an empty fifth impact sampler, a sixth impact sampler containing an acidic potassium permanganate solution, a seventh impact sampler containing an aqueous sodium hydroxide solution and an eighth impact sampler containing a silica gel, wherein the fourth impact sampler is connected via a pipe line to the cracking chamber in the pyrolysis/cracking system. ### Claim 4 (depends on 3) The device according to claim 3, wherein each of the impact samplers is a borosilicate glass bottle and is provided with a gas inlet and a gas outlet at the respective top thereof, wherein the gas inlet communicates with the inner space of the bottle through a glass tube which is provided inside the bottle and extends to the lower part of the bottle. ### Claim 5 (depends on 3) The device according to claim 3, wherein the aqueous sodium hydroxide solutions used in the air-background mercury absorption system and the mercury-sample absorption system has a concentration of 30 w/v %, and the acidic potassium permanganate aqueous solution has a potassium permanganate concentration of 1 w/v %, and an acid concentration of 10 v/v %, the acid is sulfuric acid. ### Claim 6 (depends on 1) The device according to claim 1, wherein the collection bottle with potassium permanganate absorption liquid contains a potassium permanganate absorption liquid in which mercury isotopes are absorbed, and the secondary enrichment-absorption bottle contains an acidic potassium permanganate aqueous solution, the acidic potassium permanganate aqueous solution has a potassium permanganate concentration of 1 w/v %, and an acid concentration of 10 v/v %, the acid is sulfuric acid. ### Claim 7 (depends on 1) The device according to claim 1, wherein the secondary purification-enrichment system further comprises a mercury-trapping gold tube which is disposed on a pipe line connecting the nitrogen-gas cylinder and the collection bottle with potassium permanganate absorption liquid, and approximates to the gas outlet of the nitrogen-gas cylinder. ### Claim 8 (depends on 1) The device according to claim 1, wherein the device further comprises a detector for detecting the total mercury content of the mercury enriched in the secondary enrichment-absorption bottle and a detector for detecting the composition of stable isotopes of the mercury enriched in the secondary enrichment-absorption bottle. ### Claim 9 (depends on 8) The device according to claim 8, wherein the detector for detecting the total mercury content of the mercury enriched in the secondary enrichment-absorption bottle is a cold atomic fluorescence mercury detector, and the detector for detecting the composition of stable isotopes of the mercury enriched in the secondary enrichment-absorption bottle is a multi-collector inductively-coupled plasma mass spectrometer. ### Claim 10 A method for detecting mercury isotopes in crude oil, wherein the method comprises the steps of: (1) primary enrichment: heating a crude oil sample to perform pyrolysis and cracking until the crude oil sample is completely cracked, absorbing the gas released by heating the crude oil sample with an acidic potassium permanganate aqueous solution to enrich the mercury element in the crude oil sample, and collecting all of the acidic potassium permanganate solution in which the mercury element is enriched in step (1); (2) mercury purification and enrichment: reducing the mercury absorbed in the step (1) to mercury vapor with a stannous chloride solution, and then purifying and enriching the mercury vapor by using an acidic potassium permanganate aqueous solution; (3) detecting the acidic potassium permanganate solution in which the mercury vapor is enriched in step (2) to determine the total mercury content therein; (4) detecting the acidic potassium permanganate solution in which the mercury vapor is enriched in step (2) to determine the composition/content of stable mercury isotopes therein. ### Claim 11 (depends on 10) The method according to claim 10, wherein the step (1) comprises heating the crude oil sample to the boiling point of the light hydrocarbon and holding the temperature until the light hydrocarbon volatilizes completely, and then gradiently increasing the temperature at an interval of 80 to 120° C., with each temperature gradient maintained for 20 to 40 minutes until the crude oil sample becomes a solid residue, after that subjecting the solid residue to further cracking by increasing the temperature until the cracking is complete. ### Claim 12 (depends on 10) The method according to claim 10, wherein step (1) further comprises absorbing the gas product released by heating the crude oil sample sequentially with a stannous chloride solution and an acidic potassium permanganate solution, and passing the residual gas product after the absorption into a container containing a silica gel. ### Claim 13 (depends on 10) The method according to claim 10, wherein the acidic potassium permanganate aqueous solution in step (1) has a potassium permanganate concentration of 1 w/v %, and an acid concentration of 10 v/v %, wherein the acid is sulfuric acid. ### Claim 14 (depends on 10) The method according to claim 10, wherein each of the stannous chloride solutions in step (1) and step (2) independently has a concentration of 15 to 25 w/v %. ### Claim 15 (depends on 10) The method according to claim 10, wherein step (2) comprises pumping a stannous chloride solution into the acidic potassium permanganate solution in which a crude oil is absorbed, collected in step (1), using nitrogen gas as a carry gas, to reduce mercury to mercury vapor, and feeding the mercury vapor into the acidic potassium permanganate aqueous solution with nitrogen gas to purify and enrich the mercury vapor. ### Claim 16 (depends on 15) The method according to claim 15, wherein the nitrogen gas used as a carry gas in step (2) is subjected to mercury trapping treatment prior to contacting the acidic potassium permanganate solution collected in step (1). ### Claim 17 (depends on 10) The method according to claim 10, wherein step (3) is the step of detecting the acidic potassium permanganate solution in which the mercury vapor is enriched in step (2) with a cold atomic fluorescence mercury detector; and step (4) is the step of detecting the acidic potassium permanganate solution in which the mercury vapor is enriched in step (2) with a multi-collector inductively coupled plasma mass spectrometer. ### Claim 18 (depends on 10) The method according to claim 10, wherein the method further comprises a step (5) of: comparing and analyzing the composition information for the mercury isotopes in mass fractionation and mass-independent fractionation in different types of crude oils based on the detection results in steps (3) and (4), establishing the mercury information characteristics in mass fractionation and mass-independent fractionation in different types of crude oils, and establishing an identification parameter system for crude oil genesis and evaluating the favorable exploration area. ### Claim 19 (depends on 10) The method according to claim 10, wherein the method comprises performing a detection using a device for detecting mercury isotopes in the crude oil comprising: an enrichment-absorption system and a secondary purification-enrichment system for mercury isotopes, wherein the enrichment-absorption system comprises an air-background mercury absorption system, a pyrolysis/cracking system, and a mercury-sample absorption system connected in series with pipe lines, and a vacuum pump, wherein the vacuum pump is connected to the mercury-sample absorption system through a pipe line; and wherein the secondary purification-enrichment system comprises a nitrogen-gas cylinder, a collection bottle with potassium-permanganate absorption liquid, and a secondary enrichment-absorption bottle connected in series with pipe lines, wherein the secondary purification-enrichment system further comprises a stannous-chloride storage bottle, which is connected to a pipe line between the nitrogen-gas cylinder and the collection bottle with potassium-permanganate absorption liquid via a peristaltic pump and through a pipe line.