A device and method for instant thermal treatment of milligram biomass and rapid separation and quantitative analysis of products

Abstract

This invention discloses a device and method for rapid separation and quantitative analysis of milligram-level biomass through instantaneous heat treatment, relating to the field of biomass energy utilization and analysis technology. The device includes a laser heating device, a feed inlet, a laser heater, a discharge outlet, a steam inlet, a phase change condenser, a condensing medium inlet, a distributor, a phase change material, a liquid product adsorption device, a liquid product outlet, a condensate gas outlet, a suction device, a gas delivery pipeline, a gas valve, a gas chromatography-mass spectrometry (GC-MS) instrument, and an elemental analyzer. The device is lightweight, easy to operate, and occupies a small area. It can be used alongside analytical testing equipment such as elemental analyzers and GC-MS instruments, allowing direct product analysis after milligram-level biomass raw material heat treatment. Compared to traditional analytical testing devices, the sample injection volume is increased to 1-1.5 mg, avoiding problems such as reduced chromatographic peak area, decreased detection sensitivity, and difficulty in detecting target substances at low concentrations due to insufficient sample volume.

Description

Technical Field

[0001] This invention relates to the field of biomass energy utilization and analysis testing technology, and in particular to a device and method for rapid separation and quantitative analysis of milligram-level biomass through instantaneous thermal treatment and product separation. Background Technology

[0002] Biomass combustion technology primarily involves burning biomass raw materials (such as plant straw and agricultural waste) under aerobic conditions. During combustion, the energy is converted into heat and electricity, and three-phase products (gas, liquid, and solid) are generated. Biomass pyrolysis refers to the process of transforming biomass into low-molecular-weight substances such as charcoal, liquid, and gas through thermochemical conversion under conditions of air isolation or a small supply of air.

[0003] Rapid collection and analysis of the components and their amounts in the products of combustion or pyrolysis reactions allow for the deduction of reaction mechanisms and influencing factors. Product analysis helps researchers screen for the most valuable chemical components, adjust pyrolysis process parameters, and optimize the types and composition of product components to better meet application requirements and improve the utilization efficiency of biomass resources. Furthermore, in-depth analysis of the products contributes to the development of novel biofuels and chemical products, promoting the development of biomass energy and biomass chemical products.

[0004] Currently, the analysis of combustion or pyrolysis products commonly uses small-scale devices such as tubular furnaces. Product collection and analysis often employs a stepwise, independent detection mode: after the reaction, gaseous products are collected first, then non-condensable gaseous products and condensable liquid products are separated and collected separately, and finally, solid products are collected. Subsequent analysis requires auxiliary equipment to analyze the products sealed in containers. Currently, the industry generally lacks a continuous, integrated collection and analysis process for effective product fractionation. Furthermore, the analyzable biomass mass for quantitative analysis is only about 0.2 mg, and the gas chromatography heating treatment time for biomass is too long. This leads to several problems: poor continuity of product collection and analysis, difficulty in continuous equipment operation, insufficient sample mass during analysis, resulting in reduced detection sensitivity and unstable baseline fluctuations. Summary of the Invention

[0005] To address the problems mentioned in the background art, such as poor product collection continuity, difficulty in continuous operation of analytical equipment, escape during gas-liquid product collection, low sample mass for quantitative analysis, and excessively long heating time, this invention provides a device and method for rapid separation and quantitative analysis of milligram-level biomass instantaneous pyrolysis products. This device enables continuous fractional collection and quantitative analysis of milligram-level biomass instantaneous pyrolysis products, avoiding product yield loss due to improper operation during collection. A single device can rapidly complete continuous fractional collection and high-precision quantitative analysis of products, increasing the sample volume to 1-1.5 mg, ensuring instrument sensitivity and maintaining baseline stability, and shortening the relatively long heating time in existing gas chromatography analyses.

[0006] To achieve the above objectives, the technical solution adopted by this invention is: a milligram-level biomass instantaneous heat treatment and rapid product separation and quantitative analysis device, the core components of which include: a laser heating device, a feed inlet, a feed outlet, an elemental analyzer, a phase change condenser, a liquid product adsorption device, a gas chromatography-mass spectrometry (GC-MS) instrument, a suction device, a gas delivery pipeline, a gas chromatograph, and a gas collection device. The specific layout and connection relationship of each component are as follows:

[0007] The feed inlet is connected to one side of the laser heating device and is located at the very front of the entire system, providing a raw material feeding channel. The laser heating device houses a built-in laser heater, with its front end connected to the feed inlet. A gas delivery pipe is located on the other side of the laser heating device. A solid product outlet is located below the laser heating device. A phase change condenser is connected in series at the rear of the laser heating device, connected to the gas delivery pipe of the laser heating device via a steam inlet. It contains a distributor and phase change material, and also includes a built-in liquid product adsorption device. The bottom pipe interface of the phase change condenser connects to the subsequent delivery pipeline, enabling the diversion and delivery of the condensed product. The liquid product adsorption device is connected to the gas chromatography-mass spectrometry (GC-MS) instrument. A suction device is located at the very end of the entire system and consists of a gas storage chamber, a one-way anti-backflow device, and a suction rod. The suction device is connected to the phase change condenser, GC-MS instrument, and gas chromatograph via gas delivery pipes, enabling the collection, temporary storage, and online sampling analysis of gaseous products.

[0008] The laser heater is a programmable temperature-controlled laser heating structure, which can instantly heat the milligram-level biomass raw materials to complete the combustion or pyrolysis reaction of the biomass.

[0009] A filter screen is installed at the gas delivery pipe inlet on the other side of the laser heating device to intercept solid particles, allowing only high-temperature gas-liquid mixed steam to enter the phase change condenser.

[0010] The phase change material is a plate-type phase change material. High-temperature gas-liquid mixed steam enters the phase change condenser through the steam inlet and exchanges heat with the plate-type phase change material for condensation. The heat absorbed by the plate-type phase change material can be transferred to the condensing medium in the distributor, so that the phase change material is restored and reset, and continuous cyclic cooling is achieved.

[0011] The liquid product adsorption device has a built-in oil-absorbing cotton structure, which adsorbs and collects the condensed liquid product. The oil-absorbing cotton can be detached and removed.

[0012] The suction device provides airflow power to the entire system through overall negative pressure suction. Non-condensable gases are collected in the gas storage chamber after being stabilized by a one-way anti-backflow device to avoid gas backflow affecting the reaction and detection accuracy.

[0013] The gas chromatography-mass spectrometry (GC-MS) instrument is connected to both the liquid product outlet and the gas delivery pipeline, and can simultaneously receive condensed liquid products and part of the gas products to achieve joint qualitative and quantitative analysis of gas and liquid products; the gas chromatograph automatically samples and analyzes the gas products output from the gas storage chamber online.

[0014] The solid products are directly fed into the elemental analyzer through the discharge port, enabling online detection and analysis of solid residues from biomass pyrolysis or combustion.

[0015] A method for rapid quantitative analysis of milligram-level biomass instantaneous heat treatment and its products, implemented using the aforementioned apparatus, specifically includes the following steps:

[0016] Pretreatment and equipment preheating: Before introducing biomass raw materials, the working temperature of the heater inside the laser heating device is pre-set according to the combustion or pyrolysis reaction conditions required for the experiment, and the equipment parameters are initialized.

[0017] Raw material feeding and instantaneous heat treatment: Milligram-level biomass raw materials enter through the feed port on the left side of the device and are transported to the laser heating device through the feed pipe. They are instantly heated and undergo combustion or pyrolysis reactions to generate a mixture of solid products, condensable liquid vapor, and non-condensable pyrolysis gas.

[0018] Solid product collection and analysis: After the heat treatment reaction is completed, the solid products generated by the reaction remain in the pyrolysis chamber of the laser heating device, and are then discharged from the lower outlet and directly sent to the elemental analyzer to complete the online quantitative and qualitative analysis of the solid products.

[0019] Gas-liquid mixture condensation and separation: The high-temperature gas-liquid mixture generated by the reaction is filtered through the gas delivery pipe with a filter screen on the right side of the laser heating device and then passed into the phase change condenser at the rear end; the high-temperature steam fully contacts and condenses with the phase change material in the condenser, and is separated into condensable liquid products and non-condensable gas products.

[0020] Liquid product collection and analysis: The condensable liquid products after condensation are fully adsorbed by the liquid product adsorption device inside the phase change condenser, and then transported to the gas chromatography-mass spectrometry (GC-MS) instrument to complete the online detection and component analysis of the liquid products.

[0021] Gas product collection and temporary storage: The fluid power of the entire system is provided by the terminal suction device. Under the suction action, the non-condensable pyrolysis gas after condensation and separation is continuously collected. After the gas is filtered and stabilized by the one-way anti-backflow device, it is transported to the gas storage tank for temporary storage, which effectively prevents gas backflow and ensures the continuous and stable operation of the system.

[0022] Online analysis and quantitative calculation of gaseous products: Non-condensable gases temporarily stored in the gas storage chamber are introduced into a gas chromatograph through a gas delivery pipeline. The equipment automatically completes gas sampling and online component analysis. Finally, by combining core parameters such as the effective volume of the gas storage chamber and the peak area of ​​the gas chromatogram, the accurate quantitative calculation of gaseous products is completed, realizing the rapid separation and integrated analysis of all products of biomass reaction.

[0023] The beneficial effects of this invention are:

[0024] 1. This invention provides a milligram-level biomass instantaneous heat treatment and rapid product separation and quantitative analysis device. It features a compact structure, small footprint, and is lightweight and easy to operate. It can be used alongside analytical testing equipment such as elemental analyzers and gas chromatography-mass spectrometry (GC-MS). This device can perform instantaneous testing and analysis of the reaction products directly after instantaneous heat treatment of milligram-level biomass raw materials, effectively ensuring the continuity of system operation and improving the timeliness of product detection and the accuracy of test data.

[0025] 2. The present invention provides a milligram-level biomass instantaneous heat treatment and rapid separation and quantitative analysis device, which uses laser instantaneous heating to preset the required heat treatment temperature of the laser heater and controls the feed amount at the feed inlet to 1-1.5 milligrams to achieve the purpose of instantaneous heating of biomass raw materials.

[0026] 3. The present invention provides a milligram-level biomass instantaneous heat treatment and rapid product separation and quantitative analysis device, which uses a phase change condenser to condense high-temperature steam products. The phase change heat between high-temperature steam, phase change material and condensing medium is used to condense the steam, avoiding the need for frequent condenser replacement in ordinary condensing equipment and maintaining continuous operation of the equipment. The obtained liquid products are collected by a liquid product adsorption device in the condenser, and the gaseous products are temporarily stored by a suction device to achieve efficient separation of gas and liquid products and solve the maintenance problems such as difficulty in collecting liquid products such as tar and easy contamination of experimental equipment.

[0027] 4. The present invention provides a milligram-level biomass instantaneous heat treatment and rapid product separation and quantitative analysis device, which can increase the injection volume to 1-1.5 milligrams compared with the traditional analysis and testing device with a single injection volume of 0.2 milligrams. This avoids problems such as reduced chromatographic peak area, reduced detection sensitivity, and difficulty in detecting target substances at low concentrations due to insufficient sample volume. Attached Figure Description

[0028] Figure 1 This is a schematic diagram of the structure of a milligram-level biomass instantaneous heat treatment and rapid product separation and quantitative analysis device according to the present invention.

[0029] The components include: 1. Laser heating device; 2. Feed inlet; 3. Laser heater; 4. Discharge outlet; 5. Steam inlet; 6. Phase change condenser; 7. Condensing medium inlet; 8. Distributor; 9. Phase change material; 10. Liquid product adsorption device; 11. Liquid product outlet; 12. Condensate outlet; 13. Suction device; 14. Gas delivery pipeline; 15. Gas valve; 16. Gas chromatography-mass spectrometry (GC-MS); 17. Elemental analyzer. Detailed Implementation

[0030] The present invention will now be described in further detail with reference to the accompanying drawings and specific examples.

[0031] like Figure 1 As shown, a milligram-level biomass instantaneous heat treatment and rapid product separation and quantitative analysis device includes a laser heating device 1, a feed inlet 2, a laser heater 3, a discharge outlet 4, a steam inlet 5, a phase change condenser 6, a condensing medium inlet 7, a distributor 8, a phase change material 9, a liquid product adsorption device 10, a liquid product outlet 11, a condensate gas outlet 12, a suction device 13, a gas conveying pipeline 14, a gas valve 15, a gas chromatography-mass spectrometry (GC-MS) instrument 16, and an elemental analyzer 17.

[0032] The feed inlet 2 is located at the very front of the entire device, connected to one side (e.g., the left side) of the laser heating device 1, providing a feeding channel for biomass raw materials. The laser heating device 1 contains a laser heater 3 with a preset temperature, capable of instantly heating the milligram-level biomass raw materials to achieve combustion or pyrolysis reactions. Below the laser heating device 1 is a solid product outlet 4, directly connected to the elemental analyzer 17. The solid products generated in the reaction can be discharged through this outlet and enter the elemental analyzer 17, enabling online collection and analysis of the solid products. The other side (e.g., the right side) of the laser heating device 1 is connected to a gas delivery pipe, with a filter screen at its inlet to filter the high-temperature gas-liquid mixture generated in the reaction, preventing solid particles from entering subsequent pipelines.

[0033] One side of the phase change condenser 6 is connected to the gas delivery pipe on the other side (e.g., the right side) of the laser heating device 1 via a steam inlet 5, and they are connected in series at the rear end of the laser heating device 1. A condensing medium inlet 7 is located at the top of the phase change condenser 6 for introducing the condensing medium to provide cooling conditions for the condenser. Inside the condenser, from top to bottom, are a distributor 8, a sheet-type phase change material 9, and a liquid product adsorption device 10. After entering through the condensing medium inlet 7, the condensing medium is evenly distributed in the upper part of the phase change condenser 6 by the distributor 8. The high-temperature gas-liquid mixture steam output from the laser heating device 1 enters the phase change condenser 6 through the steam inlet 5, first exchanging heat with the sheet-type phase change material 9 to cool it, resulting in a condensation phase change. The heat absorbed by the sheet-type phase change material 9 is then transferred to the condensing medium on the distributor 8, causing it to undergo a phase change and return to its initial state, thus achieving cyclic cooling. The condensed liquid product flows downwards and is collected by the liquid product adsorption device 10 located at the bottom of the phase change condenser 6. The oil-absorbing cotton inside the device efficiently adsorbs the liquid product and is easily removed and replaced, avoiding loss of liquid product during the reaction and facilitating subsequent cleaning of containers that come into contact with the liquid product. The collected liquid product is then transported from the liquid product outlet 11 at the bottom of the phase change condenser 6 to the gas chromatography-mass spectrometry (GC-MS) instrument 16 for quantitative online analysis of the liquid product. A condensate gas outlet 12 is located on the other side of the phase change condenser 6 to discharge uncondensed, non-condensable gaseous products.

[0034] The suction device 13 is located at the very end of the entire system and is connected to the condensate outlet 12 of the phase change condenser 6 via a pipeline, providing suction power for the entire system. The suction device 13 consists of a gas storage chamber, a one-way anti-backflow device, and a suction rod. The non-condensable gas after condensation enters the suction device 13 through the condensate outlet 12, and after being stabilized by the one-way anti-backflow device, it is temporarily stored in the gas storage chamber. The suction device 13 is connected to the gas chromatography-mass spectrometry (GC-MS) instrument 16 and the gas chromatograph via gas delivery pipes 14. Gas valves 15 are installed on the gas delivery pipes 14 to control the opening and closing of the gas passage and the flow rate. The gaseous products temporarily stored in the gas storage chamber can enter the gas chromatograph through the gas delivery pipes 14 for automatic sampling and online analysis. The GC-MS instrument 16 simultaneously receives liquid samples from the liquid product outlet 11 and gas samples from the gas delivery pipes 14, completing qualitative and quantitative analysis of the entire product.

[0035] A method for rapid quantitative analysis of milligram-level biomass instantaneous heat treatment and its products, implemented using the aforementioned apparatus, specifically includes the following steps:

[0036] Equipment pretreatment: Before the raw materials are introduced, the working temperature of the laser heater 3 is preset according to the reaction conditions, the condensing medium inlet 7 is opened to provide cooling conditions for the phase change condenser 6, and the equipment initialization is completed.

[0037] Raw material feeding and heat treatment: Milligram-level biomass raw materials enter the laser heating device 1 through the feed port 2 and are instantly heated under the action of the laser heater 3, undergoing combustion or pyrolysis reaction to generate a mixture of solid products, high-temperature steam and non-condensable gases; wherein, the combustion temperature is controlled at 600℃-800℃ and the pyrolysis temperature is controlled at 450℃-600℃, so as to achieve the purpose of instantaneous heating and heat treatment of milligram-level biomass.

[0038] Solid product collection and analysis: After the reaction is completed, the solid product is discharged through the lower outlet 4 and enters the elemental analyzer 17 to complete the online analysis of the solid components.

[0039] Gas-liquid mixture condensation and separation: After being filtered by the gas delivery pipe with a filter screen on the right side, the high-temperature gas-liquid mixture enters the phase change condenser 6 through the steam inlet 5. It is evenly distributed by the distributor 8 and comes into contact with the phase change material 9 for condensation, separating into condensable liquid products and non-condensable gas products.

[0040] Liquid product collection and analysis: The condensed liquid product is adsorbed by the liquid product adsorption device 10 and transported to the gas chromatography-mass spectrometry (GC-MS) instrument 16 through the liquid product outlet 11 for qualitative and quantitative analysis of the components.

[0041] Gas product collection and online analysis: Non-condensable gas enters the suction device 13 through the condensate outlet 12 and is temporarily stored in the gas storage chamber; subsequently, it enters the gas chromatograph through the gas delivery pipeline 14. Combining the gas storage chamber volume and chromatographic peak area data, the quantitative analysis of gas products is completed, realizing the rapid separation and integrated analysis of all products of biomass reaction.

Claims

1. A device for rapid quantitative analysis and separation of products from instantaneous heat treatment of milligram-level biomass, characterized in that, It includes a laser heating device (1), a feed inlet (2), a laser heater (3), a discharge outlet (4), a steam inlet (5), a phase change condenser (6), a condensing medium inlet (7), a distributor (8), a phase change material (9), a liquid product adsorption device (10), a liquid product outlet (11), a condensate outlet (12), a suction device (13), a gas delivery pipeline (14), a gas valve (15), a gas chromatography-mass spectrometry (GC-MS) instrument (16), and an elemental analyzer (17). The feed inlet (2) is located at the front end of the whole device and connected to one side of the laser heating device (1). The laser heating device (1) is equipped with a laser heater (3). The discharge port (4) is located below the laser heating device (1). The discharge port (4) is connected to the elemental analyzer (17). The other side of the laser heating device (1) is connected to the gas delivery pipe. The phase change condenser (6) is connected to the gas delivery pipe on the other side of the laser heating device (1) via a steam inlet (5) on one side. A condensing medium inlet (7) is opened at the top of the phase change condenser (6). Inside the phase change condenser (6), a distributor (8), a phase change material (9), and a liquid product adsorption device (10) are installed sequentially from top to bottom. The distributor (8) is connected to the condensing medium inlet (7), and the lower end of the distributor (8) is connected to the phase change material (9). A liquid product outlet (11) is set at the bottom of the phase change condenser (6), and a condensing gas outlet (12) is set on the other side. The liquid product outlet (11) is connected to a gas chromatography-mass spectrometry (GC-MS) instrument (16). The suction device (13) is located at the end of the entire device and is connected to the condensate outlet (12) through a pipeline. The suction device (13) includes a gas storage chamber, a one-way anti-backflow device and a suction rod. The suction device (13) is connected to the gas chromatography-mass spectrometer (16) and the gas chromatograph through a gas delivery pipeline (14). A gas valve (15) for controlling the pipeline opening and closing and the flow rate is installed on the gas delivery pipeline (14).

2. The apparatus for rapid separation and quantitative analysis of milligram-level biomass instantaneous heat treatment and products according to claim 1, characterized in that, The laser heater (3) is a programmable temperature-controlled laser heating structure, which can instantly heat the milligram-level biomass raw materials to complete the combustion or pyrolysis reaction of the biomass.

3. The apparatus for rapid separation and quantitative analysis of milligram-level biomass instantaneous heat treatment and products according to claim 1, characterized in that, A filter screen is installed at the gas delivery pipe inlet on the other side of the laser heating device (1) to intercept solid particles, allowing only high-temperature gas-liquid mixed steam to enter the phase change condenser (6).

4. The apparatus for the instant thermal treatment of milligram biomass and rapid separation and quantitative analysis of products according to claim 1, characterized in that, The phase change material (9) is a plate-type phase change material. High-temperature gas-liquid mixed steam enters the phase change condenser (6) through the steam inlet (5) and exchanges heat with the plate-type phase change material for condensation. The heat absorbed by the plate-type phase change material can be transferred to the condensing medium in the distributor (8), so that the phase change material (9) is restored and reset, and continuous cyclic cooling is achieved.

5. The apparatus for the instant thermal treatment of milligram biomass and rapid separation and quantitative analysis of products according to claim 1, characterized in that, The liquid product adsorption device (10) has a built-in oil-absorbing cotton structure, which adsorbs and collects the condensed liquid product through the oil-absorbing cotton. The oil-absorbing cotton can be detached and removed.

6. The apparatus for the instant thermal treatment of milligram biomass and rapid separation and quantitative analysis of products according to claim 1, characterized in that, The suction device (13) provides airflow power to the whole system through overall negative pressure suction. Non-condensable gas is collected in the gas storage chamber after being stabilized by the one-way anti-backflow device, so as to avoid gas backflow affecting the reaction and detection accuracy.

7. The apparatus for the instant thermal treatment of milligram biomass and rapid separation and quantitative analysis of products according to claim 1, characterized in that, The gas chromatography-mass spectrometry (GC-MS) instrument (16) is connected to both the liquid product outlet (11) and the gas delivery pipeline (14), and can simultaneously receive condensed liquid products and some gas products to achieve joint qualitative and quantitative analysis of gas and liquid products; the gas chromatograph automatically samples and analyzes the gas products output from the gas storage chamber.

8. The apparatus for rapid separation and quantitative analysis of milligram-level biomass instantaneous heat treatment and products according to claim 1, characterized in that, Solid products are directly fed into the elemental analyzer (17) through the discharge port (4) to realize online detection and analysis of solid residues from biomass pyrolysis / combustion.

9. A method for rapid separation and quantitative analysis of products from instantaneous heat treatment of milligram-level biomass, characterized in that, The device described in any one of claims 1-8 is used to implement this, specifically including the following steps: Before introducing biomass raw materials, the working temperature of the laser heater (3) inside the laser heating device (1) is pre-set according to the combustion or pyrolysis reaction conditions required for the experiment, and the equipment parameters are initialized. The milligram-level biomass raw material enters through the feed inlet (2) and is transported to the laser heating device (1) through the feed pipe. It is instantly heated and undergoes combustion or pyrolysis reaction to generate a mixture of solid products, condensable liquid vapor and non-condensable pyrolysis gas. After the heat treatment reaction is completed, the solid product generated by the reaction remains in the pyrolysis chamber of the laser heating device (1), and is then discharged from the lower outlet (4) and directly sent to the elemental analyzer (17) to complete the online quantitative and qualitative analysis of the solid product; The high-temperature gas-liquid mixture generated by the reaction is filtered through the gas delivery pipe with a filter screen on the other side of the laser heating device (1) and then introduced into the phase change condenser (6) at the rear end through the steam inlet (5). The high-temperature steam is fully contacted and condensed with the phase change material (9) in the phase change condenser (6), and is separated into condensable liquid products and non-condensable gas products. The condensable liquid products after condensation are fully adsorbed by the liquid product adsorption device (10) inside the phase change condenser, and then transported to the gas chromatography-mass spectrometry (16) to complete the online detection and component analysis of the liquid products. The fluid power of the entire device is provided by the end suction device (13). Under the suction action, the non-condensable pyrolysis gas after condensation and separation is continuously collected. After the gas is filtered and stabilized by the one-way anti-backflow device, it is transported to the gas storage chamber for temporary storage, which effectively prevents gas backflow and ensures the continuous and stable operation of the system. The non-condensable gas temporarily stored in the gas storage chamber is introduced into the gas chromatograph through the gas delivery pipeline (14). The equipment automatically completes gas sampling and online component analysis. Finally, by combining the effective volume of the gas storage chamber and the peak area of ​​the gas chromatogram, the accurate quantitative calculation of the gas products is completed, realizing the rapid separation and integrated analysis of all products of the biomass reaction.

10. The method of claim 9, wherein, The combustion temperature is controlled at 600℃-800℃, and the pyrolysis temperature is controlled at 450℃-600℃.

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