阅读说明：本技术 高分子材料在海洋环境中的降解性能检测装置 (Degradation performance detection device of high polymer material in marine environment ) 是由 王格侠 季君晖 甄志超 李飞 黄丹 卢波 于 2020-05-15 设计创作，主要内容包括：本发明公开了一种检测高分子材料在海水环境中的生物降解性能的装置,其包括：降解反应单元；氧气供应单元；CO-(2)气体的吸收单元,用于吸收降解反应单元产生的CO-(2),使其生成碳酸根离子；碳酸根离子测定单元(例如阴离子色谱仪)；取样单元,用于提取吸收样液并输送至碳酸根离子测定单元；此外,本发明的检测装置还包括控制单元,对取样单元进行控制,因此,本发明的检测装置不仅具有高灵敏度和高检测限,而且能够实现取样和样液输送的自动化,此外,还可增设预警单元,通过控制单元对降解反应条件以及各单元运行状况进行自动监测和预警。(The invention discloses a device for detecting biodegradability of a high polymer material in a seawater environment, which comprises: a degradation reaction unit; an oxygen supply unit; CO 2 2 An absorption unit for gas for absorbing CO generated by the degradation reaction unit 2 Generating carbonate ions; a carbonate ion measuring unit (e.g., an anion chromatograph); the sampling unit is used for extracting the absorption sample liquid and conveying the absorption sample liquid to the carbonate ion measuring unit; in addition, the detection device also comprises a control unit for controlling the sampling unit, so that the detection device not only has high sensitivity and high detection limit, but also can realize the automation of sampling and sample liquid conveying, and in addition, an early warning unit can be additionally arranged, and the control unit can automatically monitor and early warn the degradation reaction conditions and the operation conditions of all units.)

1. The device for detecting the biodegradability of a polymer material in a seawater environment comprises:

a degradation reaction unit comprising at least one degradation reaction vessel;

an oxygen supply unit for supplying an oxygen-containing but carbon dioxide-free gas to the at least one degradation reaction vessel;

the carbon dioxide gas absorption unit comprises absorption hydrazine and is used for absorbing the carbon dioxide gas generated by the degradation reaction unit to generate carbonate ions; wherein each degradation reaction container corresponds to at least one absorption hydrazine;

a carbonate ion determination unit for determining the content of carbonate ions generated in the at least one absorption hydrazine;

a sampling unit for performing the following sampling operations: and extracting an absorption sample liquid from the at least one absorption hydrazine and conveying the absorption sample liquid to the carbonate ion measuring unit.

2. The detection apparatus of claim 1, wherein the carbonate ion determination unit comprises an anion chromatograph having an autosampler.

3. The detection apparatus according to claim 1 or 2, further comprising a control unit arranged to: controlling the sampling unit to synchronously sample from the at least one absorption hydrazine according to a preset sampling time interval.

4. The detection apparatus of claim 3, the control unit further configured to: and acquiring a current carbonate ion measurement value measured by the carbonate ion measurement unit, and adjusting the sampling time interval of the sampling unit based on the current carbonate ion measurement value.

5. The detection apparatus of claim 3, the sampling unit comprising:

a throttle valve corresponding to each of the at least one absorption hydrazine, wherein a control unit is provided to control the sampling operation by controlling opening and closing of the throttle valve;

and an absorption sample liquid delivery subunit for delivering the absorption sample liquid discharged from the throttle valve to the carbonate ion measurement unit.

6. The detecting device according to claim 5, wherein the absorption sample liquid delivering subunit comprises a flow peristaltic pump, and the control unit is further configured to control the sampling operation by controlling the flow peristaltic pump.

7. The detecting device for detecting the concentration of hydrazine in water as claimed in claim 3, wherein each degradation reaction vessel corresponds to at least two absorption hydrazines, and the absorption hydrazines are connected in series with each other.

8. The detection apparatus according to claim 3, wherein the oxygen supply unit includes:

an air compressor;

the buffer tank is used for buffering compressed air;

at least one carbon dioxide gas absorbs hydrazine for removing carbon dioxide gas from the air supplied by the air compressor.

9. The detection apparatus of claim 8, further comprising:

an early warning unit;

a sensing assembly disposed at least one absorption hydrazine of the degradation reaction unit for sensing a degradation reaction condition;

wherein the control unit is further configured to: and receiving the degradation reaction condition sensed by the sensing assembly, and controlling the early warning unit to send out an early warning signal when the degradation reaction condition is determined to be abnormal.

10. The detection apparatus of claim 9, wherein the detection apparatus further comprises: a pH meter disposed in at least one carbon dioxide gas absorbing hydrazine in the oxygen supply unit, the control unit further configured to: and receiving the pH value measured by the pH meter, and controlling the early warning unit to send out an early warning signal when the pH value exceeds a set threshold value.

Technical Field

The present invention relates to a device for detecting biodegradability of a polymer material, and more particularly, to a device for detecting biodegradability of a polymer material in a marine environment.

Background

The degradation of the polymer material is classified into photodegradation, oxidative degradation, hydrolysis, biodegradation, light/oxygen degradation and the like according to a degradation mechanism, wherein biodegradation is the most concerned degradation mode and the most widely applied degradation mode, and biodegradation generally takes carbon dioxide gas finally generated by the polymer material in a medium as a core evaluation standard. Therefore, in the prior art, the biodegradation performance of the material is evaluated by detecting the release amount of carbon dioxide in the degradation process of the high polymer material.

In a real marine degradation environment, the highest temperature does not exceed 30 ℃, the seawater temperature gradually decreases with the increase of the water depth, and the seabed temperature is lower than 10 ℃. Because the temperature of the marine environment is lower, the degradation of the high polymer material in the seawater environment is slower, and the amount of carbon dioxide released by degradation in unit time is less. For detecting the biodegradation performance of the high polymer material, the existing detection device usually adopts a respirometer, an infrared spectrometer or an acid-base titration method to detect the carbon dioxide generated in the degradation process, wherein, the detection limits of the respirometer and the infrared spectrometer are both above 1ppm, the detection limits of the two detection instruments are higher, and the two detection instruments are only suitable for testing a large amount of carbon dioxide generated by the degradation of high molecular materials under the conditions of high microorganism content and high temperature such as compost, however, in a real marine degradation environment, because the temperature of the degradation environment is lower and the degradation of the high polymer material is slower, the amount of carbon dioxide released by the degradation in unit time is lower, the detection limits of the respirometer and the infrared spectrometer are high, and when the amount of the carbon dioxide released by degradation is lower than the detection limit, the carbon dioxide cannot be detected, so that the degradation performance is easily subjected to wrong evaluation. In addition, the acid-base titration method needs to frequently prepare and replace alkali liquor and titrate with standard solution, so that experimental error sources are many, errors are easily caused by more human factors, in addition, manpower is consumed, the detection efficiency is low, and the degradation of the high-molecular material in the marine environment cannot be efficiently, accurately and sensitively evaluated.

Therefore, there is a need for a detection device with higher sensitivity and capable of realizing automation, which is suitable for detecting the biodegradation performance of the polymer material in the marine environment.

Disclosure of Invention

In view of the above problems in the prior art, the present invention is directed to an improved apparatus for detecting biodegradability of a polymer material in a marine environment, which not only can improve detection sensitivity, but also can realize automatic detection, and truly reflect degradability of the polymer material in the marine environment.

The device for detecting the biodegradability of the high polymer material in the marine environment comprises:

a degradation reaction unit comprising at least one degradation reaction vessel;

an oxygen supply unit for supplying an oxygen-containing but carbon dioxide-free gas to the at least one degradation reaction vessel;

the carbon dioxide gas absorption unit comprises absorption hydrazine and is used for absorbing the carbon dioxide gas generated by the degradation reaction unit to generate carbonate ions; wherein each degradation reaction container corresponds to at least one absorption hydrazine;

a carbonate ion determination unit for determining the content of carbonate ions generated in the at least one absorption hydrazine;

a sampling unit for performing the following sampling operations: and extracting an absorption sample liquid from the at least one absorption hydrazine and conveying the absorption sample liquid to the carbonate ion measuring unit.

In some embodiments of the invention, the carbonate ion determination unit comprises an anion chromatograph having an autosampler.

In some embodiments of the invention, the detection device further comprises a control unit configured to: controlling the sampling unit to synchronously sample from the at least one absorption hydrazine according to a preset sampling time interval.

In some embodiments of the invention, the control unit is further configured to: and acquiring a current carbonate ion measurement value measured by the carbonate ion measurement unit, and adjusting the sampling time interval of the sampling unit based on the current carbonate ion measurement value. For example, the control unit is arranged to: the sampling time interval at the early stage of degradation detection is larger than that at the later stage of degradation.

In some embodiments of the invention, the sampling unit comprises:

a throttle valve corresponding to each of the at least one absorption hydrazine, wherein the control unit is configured to control the sampling operation by controlling opening and closing of the throttle valve;

and an absorption sample liquid delivery subunit for delivering the absorption sample liquid discharged from the throttle valve to the carbonate ion measurement unit.

In some embodiments of the present invention, the absorption sample liquid delivery subunit comprises a flow peristaltic pump, and the control unit is further configured to control the sampling operation by controlling the flow peristaltic pump.

In some embodiments of the present invention, each degradation reaction vessel corresponds to at least two absorption hydrazines, and the absorption hydrazines are connected in series, so as to improve the absorption efficiency of carbon dioxide.

In some embodiments of the invention, the oxygen supply unit comprises:

an air compressor;

the buffer tank is used for buffering compressed air;

at least one carbon dioxide gas absorbs hydrazine for removing carbon dioxide gas from the air supplied by the air compressor.

In some embodiments of the invention, the detection device further comprises:

an early warning unit;

a sensing assembly disposed at least one absorption hydrazine of the degradation reaction unit for sensing a degradation reaction condition;

wherein the control unit is further configured to: and receiving the degradation reaction condition sensed by the sensing assembly, and controlling the early warning unit to send out an early warning signal when the degradation reaction condition is determined to be abnormal.

In some embodiments of the invention, the detection device further comprises: a pH meter disposed in at least one carbon dioxide gas absorbing hydrazine in the oxygen supply unit, the control unit further configured to: and receiving the pH value measured by the pH meter, and controlling the early warning unit to send out an early warning signal when the pH value exceeds a set threshold value.

Compared with the existing device for detecting the biodegradability of the high polymer material in the marine environment, the device adopts the degradation absorption unit to absorb carbon dioxide released by degradation to generate carbonate ions, calculates the accumulated release amount of the carbon dioxide based on the content of the carbonate ions measured by the carbonate ion measuring unit, has high sensitivity and high detection limit when the content of the carbonate ions is measured by an anion chromatograph, can realize detection automation when the detection device is provided with the control unit, can automatically sample from the carbon dioxide absorption unit according to the instruction of the control unit, and conveys the absorption sample liquid to the carbonate ion measuring unit.

Drawings

Fig. 1 shows a schematic configuration diagram of a biodegradation property detection apparatus according to an exemplary embodiment of the present invention.

Detailed Description

The present invention will be described in detail with reference to specific examples, which are provided for illustration only and do not limit the scope of the present invention.

Fig. 1 shows a schematic view of a detection apparatus for detecting biodegradability of a high molecular material in a seawater environment according to an exemplary embodiment of the present invention. As can be seen from the figure, the apparatus includes: the degradation reaction unit 1, the oxygen supply unit 2, the carbon dioxide gas absorption unit 3, the carbonate ion measurement unit 4, the sampling unit 5, the control unit 6, and the early warning unit 7, which will be described in detail below.

The degradation reaction unit 1 in this embodiment includes at least one degradation reaction vessel, and for convenience of illustration, only three degradation reaction vessels are shown in the figure, that is, the degradation reaction vessel 11a, the degradation reaction vessel 11b, and the degradation reaction vessel 11c, and a person skilled in the art can select an appropriate number of degradation reaction vessels according to actual needs, where the degradation reaction vessels are used to hold a detection solution simulating a seawater environment, that is, a detection solution containing microorganisms and inorganic nutrients thereof, and oxygen-containing gas is introduced to form an aerobic degradation environment.

The oxygen supply unit 2 in this embodiment supplies oxygen-containing gas to the degradation reaction vessel to allow the degradation reaction to proceed in an aerobic degradation environment. As can be seen from FIG. 1, the unit comprises an air compressor 21, a gas buffer tank 22 and a carbon dioxide absorption hydrazine, wherein the air compressor 21 blows air into CO₂Absorbing hydrazine to remove CO in the hydrazine₂Gas, CO removal₂Air of the gas is slowly introduced into the degradation reaction vessel, and the oxygen supply unit of the present embodiment is provided with a gas buffer tank 22 and a gas flow meter in the gas flow path in order to appropriately control the gas flow rate. Specifically, the compressed air is branched by the flow divider 24 via the gas buffer tank 22, and the branched air enters the absorption hydrazine 25a, the absorption hydrazine 25b, and the absorption hydrazine 25c via the flow meter 23a, the flow meter 23b, and the flow meter 23c, respectively. These absorption hydrazines are used to remove carbon dioxide gas from the compressed air so as not to affect the accuracy of the measurement of the carbon dioxide gas produced by the degradation reaction unit. In order to ensure complete removal of carbon dioxide gas from the compressed air, the pH of the absorption solution in each absorption hydrazine can be monitored so that it can be added immediately before the absorption base solution is used up. In this embodiment, 2 absorbing hydrazines are provided in series for each gas flow path, and a larger number of absorbing hydrazines may be selected and used in series as needed to sufficiently remove carbon dioxide from compressed air. In alternative embodimentsIn the formula, the oxygen supply unit can also directly adopt an oxygen source to supply oxygen without arranging an absorption hydrazine for removing carbon dioxide gas.

In this embodiment, the absorption unit 3 for absorbing carbon dioxide generated by the degradation reaction includes at least one absorption hydrazine, and when the degradation detection of the polymer material is performed, CO generated by the degradation reaction₂Collecting gas by absorbing hydrazine with alkali solution, absorbing CO with alkali solution in hydrazine₂The gas generates carbonate ions, and the alkali solution is preferably a solution which can easily and rapidly generate water-soluble carbonate ions with carbon dioxide, for example, a NaOH solution or a KOH solution with a proper concentration is selected. For ease of illustration, in fig. 1, only one absorbing hydrazine is shown for each degradation reaction vessel, namely: the degradation reaction container 11a correspondingly absorbs the hydrazine 31a, the degradation reaction container 11b correspondingly absorbs the hydrazine 31b, and the degradation reaction container 11c correspondingly absorbs the hydrazine 31 c. In an alternative embodiment, a plurality of absorption hydrazines connected in series with each other may be provided corresponding to each degradation reaction vessel as necessary to improve absorption efficiency.

The carbonate ion measuring unit 4 in the present embodiment includes an anion chromatograph 41 having an autosampler 42 for measuring the content of carbonate ions generated by absorption of carbon dioxide gas generated by degradation reaction by an alkali solution absorption hydrazine. In the embodiment, the anion chromatograph is adopted to measure the content of carbonate ions in the hydrazine absorption solution and calculate the CO generated by degradation₂When a plurality of absorption hydrazines are used in series, the sum of the absorption amounts of the absorption hydrazines in the same degradation period is calculated. Cumulative generation of CO from degradation₂The percentage of the gas quantity in the theoretical carbon dioxide generation quantity of the seawater degraded plastics is the degradation rate or mineralization rate.

The sampling unit 5 in this embodiment extracts an absorption sample liquid from at least one absorption hydrazine and sends the absorption sample liquid to the carbonate ion measuring unit 4. The sampling unit 5 comprises a throttle valve 51a, a throttle valve 51b and a throttle valve 51c which respectively correspond to the absorption hydrazine 31a, the absorption hydrazine 31b and the absorption hydrazine 31c, and samples the absorption solution in the corresponding absorption hydrazine through opening and closing of the throttle valves.

The sampling unit 5 in this embodiment further includes an absorption sample liquid delivery subunit, configured to deliver the absorption sample liquid discharged from the throttle valve to the carbonate ion determination unit 4, where the absorption sample liquid delivery subunit includes a flow peristaltic pump 52a, a flow peristaltic pump 52b, and a flow peristaltic pump 52c, and is respectively configured to deliver the absorption sample liquid discharged from the throttle valve 51a, the throttle valve 51b, and the throttle valve 51c, and deliver the absorption sample liquid to the autosampler 42 of the anion chromatograph 41. It will be appreciated by those skilled in the art that other similar fluid delivery devices may be used to deliver the absorption sample to the autosampler of the anion chromatograph.

When the detection device of the embodiment is used for detecting the degradation performance of the polymer material, the concentration of carbonate ions is measured by an anion chromatograph, in order to analyze the change relationship of the degradation performance along with time, the content of the accumulated generated carbonate ions is periodically measured in the degradation process, then the accumulated release amount of corresponding carbon dioxide is calculated, and finally the mineralization rate (namely, the degradation rate) of the detected polymer material is calculated to evaluate the biodegradation degree.

The extent of biodegradation of the sample can be assessed by calculating the mineralization rate (see equation 1):

wherein (CO)₂)_TCumulative CO production for the sample₂Content of (g), (CO)₂)_BCumulative CO production for blank set₂Content (mg) and ThCO₂Theoretical generation of CO for a sample₂Total content (mg) (see equation 2).

In the formula M_TOTTo test the total dry solids (mg) of the material, C_TOTTo test the total organic carbon content (%)

The control unit 6 in the present embodiment is arranged to perform the following operations: specifically, the control unit controls the opening and closing of the corresponding throttle valves 51a, 51b, and 51c to sample the absorption sample liquid discharged from the throttle valves 51a, 51b, and 51c, and the flow rate control peristaltic pumps 52a, 52b, and 52c are supplied to the autosampler 42 of the anion chromatograph 41 to measure carbonate ions.

The control unit in this embodiment may be further configured to: the current carbonate ion measurement value measured by the carbonate ion measurement unit 4 is acquired, and the sampling time interval of the sampling unit 5 is adjusted based on the current carbonate ion measurement value. For example, at a stage where the degradation reaction rate is slow, the content of carbonate ions measured by the measuring unit 4 is small, so that the sampling time interval can be appropriately extended and the sampling frequency can be reduced; and for the stage that the degradation reaction speed is higher, the carbonate ion content measured by the measuring unit 4 is higher, so that the sampling time interval of the sampling unit can be properly shortened, the sampling frequency is increased, the detection efficiency is improved, and the detection result can reflect the degradation process more truly.

In order to warn about possible abnormal situations during degradation detection, the detection device of the present embodiment further includes a warning unit 7, and accordingly, a sensing component is disposed for an object to be monitored, for example, a pH meter (not shown in the figure) is disposed in the carbon dioxide absorption hydrazine of the oxygen supply unit, and the control unit 6 is configured to: and receiving the pH value measured by the pH meter, and controlling the early warning unit 7 to send out an early warning signal when the pH value exceeds a set threshold value. For example, when the absorption hydrazine is exhausted and the carbon dioxide in the compressed air cannot be continuously and effectively removed, the pH value exceeds a set threshold value, the control unit controls the early warning unit to send out an early warning signal, and the early warning signal can be a conventional sound signal, a vibration signal or a luminous signal and the like, so as to remind a user of timely updating the absorption liquid in the absorption hydrazine.

In addition, the detection device of this embodiment may further include a sensing component (not shown in the figure) disposed on the hydrazine absorption of the degradation reaction unit, for sensing the degradation reaction condition, such as a degradation temperature sensor, a pH meter, a salinity meter, a gas pressure sensor, and the like, for sensing whether the degradation reaction condition is abnormal, and the control unit 6 is configured to: and receiving the degradation reaction condition sensed by the sensing assembly, and controlling the early warning unit to send out an early warning signal when the degradation reaction condition is determined to be abnormal.

According to the above specific embodiments, when the detection device of the present invention is used to detect the degradation performance of a polymer material in a marine environment, an alkaline solution absorbs hydrazine to collect carbon dioxide generated by degradation of the polymer material, and converts the carbon dioxide into carbonate ions, and a carbonate ion determination unit (e.g., an anion chromatograph) is used to determine the content of the carbonate ions in the absorbed hydrazine solution, and the accumulated amount of the carbon dioxide released within the degradation duration is obtained by conversion based on the content of the carbonate ions, and the detection limit is significantly lower than the detection limits of an infrared spectrometer and a gas chromatograph used in the prior art, so that the detection sensitivity is high, and the detection device is particularly suitable for detecting the degradation performance of the polymer material in a seawater environment. For an infrared spectrometer and a gas chromatograph, carbon dioxide gas is directly measured, and the measurement of the carbon dioxide gas generated cumulatively within a long degradation period is not only restricted by a high detection limit, but also limited by the volume of a gas container, so that the degradation performance of the high polymer material in a seawater environment with slow degradation is not easy to accurately measure. The acid-base titration method is influenced by various human factors, has a plurality of detection result errors and can not reflect the degradation performance of the real marine environment. In addition, the detection device provided by the invention is provided with the control unit, so that the automatic detection, monitoring and early warning can be realized

The present invention has been described in detail with reference to the specific embodiments, which are exemplary only, and are not intended to limit the scope of the present invention, and those skilled in the art may make various modifications, changes, or alterations to the various features of the present invention without departing from the spirit and scope of the present invention. Therefore, various equivalent changes made in accordance with the present invention are also within the scope of the present invention.