阅读说明：本技术 一种可在线监控的吸附设备 (Adsorption equipment capable of being monitored on line ) 是由 李俊诚 钱震 张晓龙 武靖为 高源� 邬学霆 陈浩庭 于 2019-03-04 设计创作，主要内容包括：本发明涉及一种可在线监控的吸附设备。吸附设备包括在线中红外光谱检测系统,在需要在线监控的物料管路上设置带有测试样品池的支路,采用在线中红外光谱仪对样品池中的物料进行检测。本发明的可在线监控的吸附设备能够对吸附设备中的物料浓度进行实时在线检测。(The invention relates to adsorption equipment capable of being monitored on line. The adsorption equipment comprises an online mid-infrared spectrum detection system, a branch with a test sample pool is arranged on a material pipeline to be monitored online, and an online mid-infrared spectrometer is adopted to detect materials in the sample pool. The adsorption equipment capable of being monitored on line can carry out real-time on-line detection on the concentration of the materials in the adsorption equipment.)

1. An adsorption equipment that can on-line monitoring which characterized in that: the adsorption equipment comprises an online mid-infrared spectrum detection system, a branch with a test sample pool is arranged on a material pipeline to be monitored online, and an online mid-infrared spectrometer is adopted to detect materials in the sample pool.

2. The on-line monitorable adsorbent device of claim 1 and wherein: the mid-infrared spectrometer adopts an optical fiber probe type measurement, and the spectral range is 4000-650cm^-1Resolution of 4cm^-1。

3. An on-line monitorable adsorption apparatus according to claim 1 or claim 2 and wherein: the mid-infrared spectrum detection system is arranged on an inlet pipeline and an outlet pipeline of the adsorption equipment.

4. The on-line monitorable adsorbent device of claim 3 and wherein: furthermore, the adsorption equipment comprises a plurality of adsorption columns, and an online mid-infrared spectrum detection system is arranged on an inlet pipeline and an outlet pipeline of each adsorption column.

5. An on-line monitorable adsorption apparatus according to any one of claims 1 to 4 and wherein: an inlet pipe and an outlet pipe which are led out to enter the sample cell respectively before and after a regulating valve with pressure difference in a material pipeline; the pressure in the cell was regulated by a valve to be below 69bar and the temperature of the feed to the cell was not higher than 200 ℃.

6. The on-line monitorable adsorbent device of claim 2 and wherein: and performing spectral scanning through the optical fiber probe, and processing through an instrument software workstation to obtain the spectral peak height under the characteristic wavelength.

7. An on-line monitorable adsorption apparatus according to any one of claims 1 to 6 and wherein: the adsorption equipment is simulated moving bed equipment.

8. The on-line monitorable adsorbent device of claim 7 and wherein: the simulated moving bed equipment comprises an adsorption bed, a raw material feeding system, a desorbent feeding system, a circulating system, a liquid pumping system, a raffinate pumping system, a program control valve group and an automatic control system; wherein, the adsorption bed comprises a plurality of adsorption columns which are divided into an adsorption area, a purification area and a desorption area;

the upper end of each adsorption column is provided with a raw material feed valve, a desorbent feed valve and a circulating liquid feed valve;

the lower end of each adsorption column is provided with a raffinate discharge valve and an extract discharge valve;

a one-way valve is arranged between every two adjacent adsorption columns;

the raw material feeding system is connected with a raw material feeding valve of each adsorption column;

the desorbent feed system is connected with a desorbent feed valve of each adsorption column;

the circulating system comprises a circulating pump, and is connected with a circulating liquid feeding valve of each adsorption column through the circulating pump;

the extract system is connected with an extract discharge valve of each adsorption column;

the raffinate system is connected with a raffinate discharge valve of each adsorption column;

all valves form a program control valve group, the program control valve group is connected with an automatic control system, and the automatic control system can control the opening and closing state of each valve in the program control valve group.

9. An on-line monitorable adsorption apparatus according to any one of claims 1 to 8 and wherein: the detection steps of the intermediate infrared spectrometer are as follows:

(1) calibration model establishment

Selecting various Fischer-Tropsch synthesis oil samples, and determining the contents of olefin, alkane and alkyne in the Fischer-Tropsch synthesis oil samples by adopting a gas chromatography; and then, performing mid-infrared spectrum scanning on each sample through a sample cell, and selecting C-C bond at 3100-3010 cm^-1Is a characteristic spectral region; the C-C bond is 2975-2800 cm^-1Is a characteristic spectral region; the C ≡ C bond is 3300-2150 cm^-1Relating the response value of the characteristic spectrum region with the contents of alkene, alkane and alkyne of a sample determined by adopting a gas chromatography, and respectively establishing a correction model by adopting a least square method of a stoichiometric method;

(2) determination of unknown sample content

Performing mid-infrared spectrum scanning on an unknown sample under the same test condition as that of the calibration model, wherein the mid-infrared spectrum scanning is respectively 3100-3010 cm^-1、2975～2800cm^-1、3300～2150cm^-1And substituting the response values of the spectral regions into the corresponding correction models to obtain the contents of the olefin, the alkane and the alkyne in the unknown sample.

10. An on-line monitorable adsorption apparatus according to claim 4 or claim 8 and wherein: the number of the adsorption columns is 3-100.

Technical Field

The invention belongs to the technical field of adsorption separation, and particularly relates to adsorption equipment capable of being monitored on line.

Background

Adsorption equipment is a commonly used separation equipment. The adsorption equipment comprises fixed bed adsorption equipment, simulated moving bed equipment and the like. The simulated moving bed equipment has the advantages of high production efficiency, less organic solvent consumption, large mass transfer driving force, convenience for automatic continuous production and the like, is widely applied to the fields of petrochemical industry, food industry, pharmacy and the like, and is a complex industrial process and a periodic process with a plurality of influences, such as nonlinearity, nonequilibrium, nonideal and multiple degrees of freedom.

The simulated moving bed divides the fixed adsorption bed into a plurality of sections, the sections are filled with adsorbents, and liquid between the sections can not directly flow through. Each section is provided with an inlet and outlet pipeline, and the inlet and outlet of the inlet and outlet pipelines are controlled by a multi-channel rotary valve. Typically, in a simulated moving bed with 8 adsorption columns, 20 of 24 inlets and outlets only play a role in connection between sections, the other 4 inlets and outlets are used for the inlet or outlet of four strands of materials, the positions of the inlets and outlets of the materials at a certain moment divide the whole adsorption bed layer into four zones, the distances of the zones are unequal, and the mass transfer of each zone is different.

The simulated moving bed uses a multi-channel rotary valve to move the inlet and outlet of four materials upward at a speed synchronous with the change of solid-phase concentration. Thus, a closed loop is formed, the total result is basically the same as the effect of keeping the position of the inlet and the outlet still, and the effect of moving the solid adsorbent from top to bottom in the adsorber is basically the same, so that the separation effect is achieved. The core equipment for realizing the process is a multi-channel rotary valve, and the flow is periodically switched by the rotation of the multi-channel rotary valve, so that the aim of separating products is fulfilled.

Disclosure of Invention

In order to solve the technical problem, the invention provides adsorption equipment capable of being monitored on line, which can be used for detecting the concentration of materials in the adsorption equipment on line in real time.

The adopted technical scheme is as follows:

an adsorption device capable of being monitored on line comprises an on-line mid-infrared spectrum detection system, a branch with a test sample pool is arranged on a material pipeline needing on-line monitoring, and an on-line mid-infrared spectrometer is adopted to detect materials in the sample pool.

Preferably, the content of olefin, alkane and alkyne in the material of the adsorption device can be detected in real time by adopting an online mid-infrared spectrum detection system.

The mid-infrared spectrometer adopts an optical fiber probe type measurement, and the spectral range is 4000-650cm^-1Resolution of 4cm^-1。

The mid-infrared spectrum detection system may be located on the inlet and outlet lines of the adsorption device.

Furthermore, the adsorption equipment comprises a plurality of adsorption columns, and an online mid-infrared spectrum detection system can be arranged on the inlet and outlet pipelines of each adsorption column.

An inlet pipe and an outlet pipe which are led out to enter the sample cell respectively before and after a regulating valve with pressure difference in a material pipeline; the pressure in the cell was regulated by a valve to be below 69bar and the temperature of the feed to the cell was not higher than 200 ℃.

And performing spectral scanning through the optical fiber probe, and processing through an instrument software workstation to obtain the spectral peak height under the characteristic wavelength.

Preferably, the feed to the adsorption unit is from Fischer-Tropsch oil.

The detection steps of the infrared spectrometer in the invention are as follows:

(1) calibration model establishment

Selecting various Fischer-Tropsch synthesis oil samples, and determining the contents of olefin, alkane and alkyne in the Fischer-Tropsch synthesis oil samples by adopting a gas chromatography; then, the samples are subjected to mid-infrared spectrum scanning through a sample cell, and C-C bond is selected to be 3100-3010 cm^-1Is a characteristic spectral region; the C-C bond is 2975-2800 cm^-1Is a characteristic spectral region; the C ≡ C bond is 3300-2150 cm^-1Relating the response value of the characteristic spectrum region with the contents of alkene, alkane and alkyne of a sample determined by adopting a gas chromatography, and respectively establishing a correction model by adopting a least square method of a stoichiometric method;

(2) determination of unknown sample content

Performing mid-infrared spectrum scanning on an unknown sample under the same test condition as that of the calibration model, wherein the mid-infrared spectrum scanning is respectively 3100-3010 cm^-1、2975～2800cm^-1、3300～2150cm^-1And substituting the response values of the spectral regions into the corresponding correction models to obtain the contents of the olefin, the alkane and the alkyne in the unknown sample.

Preferably, the step of establishing the correction model by using the least square method of the chemometric method comprises the following steps:

(1) assuming that the spectral peak height y of an olefin (or an alkane or an alkyne) at a characteristic wavelength is in the following relation with the concentration value x of the olefin (or the alkane or the alkyne), wherein y is ax + b, a is a coefficient and b is an intercept.

(2) There is a correspondence for each set of data (xi, yi).

(3) Error e ═ yi- (axi + b)

(4) When in useThe minimum degree of fitting is the highest, i.e.

Minimum, S stands for standard deviation (5) and first order partial derivatives are calculated respectively

(6) Let the above two formulae equal 0, respectively, have

(7) Finally obtaining the final product

(8) Substituting the values x and y of each sample to obtain a value a and a value b, and further obtaining a linear relation equation.

The adsorption unit of the present invention is preferably a simulated moving bed unit and preferably has the following structure:

the simulated moving bed equipment comprises an adsorption bed, a raw material feeding system, a desorbent feeding system, a circulating system, a liquid pumping system, a raffinate pumping system, a program control valve group and an automatic control system; wherein, the adsorption bed comprises a plurality of adsorption columns which are divided into an adsorption area, a purification area and a desorption area;

the upper end of each adsorption column is provided with a raw material feed valve, a desorbent feed valve and a circulating liquid feed valve;

the lower end of each adsorption column is provided with a raffinate discharge valve and an extract discharge valve;

a one-way valve is arranged between every two adjacent adsorption columns;

the raw material feeding system is connected with a raw material feeding valve of each adsorption column;

the desorbent feed system is connected with a desorbent feed valve of each adsorption column;

the circulating system comprises a circulating pump, and is connected with a circulating liquid feeding valve of each adsorption column through the circulating pump;

the extract system is connected with an extract discharge valve of each adsorption column;

the raffinate system is connected with a raffinate discharge valve of each adsorption column;

all valves form a program control valve group, the program control valve group is connected with an automatic control system, and the automatic control system can control the opening and closing state of each valve in the program control valve group.

Preferably, the number of the adsorption columns is 3-100.

Preferably, the adsorption columns are 8 × N, wherein N is an integer greater than or equal to 1.

Preferably, the raw material feeding system comprises a raw material pump and a raw material heater positioned at the downstream of the raw material pump, and an outlet pipeline of the raw material heater is connected with the adsorption column;

the desorbent feed system comprises a desorbent pump and a desorbent heater positioned at the downstream of the desorbent pump, and an outlet pipeline of the desorbent heater is connected with the adsorption column;

the extract system comprises an extract pump, and the extract pump is connected with an extract pipeline of the adsorption bed;

the raffinate system comprises a raffinate pump, and the raffinate pump is connected with a raffinate pipeline of the adsorption bed;

and a feed inlet of a circulating pump of the circulating system is connected with an extract liquid pipeline of the adsorption bed.

Preferably, the valve types in the program control valve group are respectively and independently selected from one of a ball valve, a needle valve, a stop valve and a butterfly valve. Preferably, the actuator is pneumatic or electric.

Preferably, the relative position of the circulation pump in the region is constant.

Preferably, the connecting lines between each adsorption column have the same volume.

Preferably, each adsorption column has the same volume of lines connected to the circulation pump.

Preferably, the adsorption zone further comprises a buffer zone, i.e., the adsorption bed is divided into an adsorption zone, a purification zone, a desorption zone and a buffer zone.

The high-efficiency simulated moving bed process using the high-efficiency simulated moving bed equipment comprises the following steps:

the efficient simulated moving bed process using the efficient simulated moving bed equipment has the advantages that the valve is controlled to be switched to change the position of feeding and discharging materials each time, and the simulated movement of an adsorption zone, a purification zone and a desorption zone is realized.

Preferably, the valves are controlled to be switched to change the position of feeding and discharging materials each time, so that the simulated movement of the adsorption area, the purification area, the desorption area and the buffer area is realized.

Preferably, the number of the adsorption columns is 8, and the efficient simulated moving bed process specifically comprises the following steps:

in the 0-t time sequence, opening a check valve A1 and a desorbent feed valve A2 of an adsorption column 1, a desorbent feed valve B2 and an extract liquid discharge valve B6 of the adsorption column 2, a circulating liquid feed valve C4 of the adsorption column 3, a check valve D1 of the adsorption column 4, a check valve E1 of the adsorption column 5, a raw material feed valve E3, a check valve F1 of the adsorption column 6, a raffinate discharge valve F5, a check valve G1 of the adsorption column 7 and a check valve H1 of the adsorption column 8, and closing the other valves;

at the moment, the adsorption area is an adsorption column 5 and an adsorption column 6, raw materials enter the adsorption column 5 and the adsorption column 6 to adsorb target product components, and non-target components flow out from an outlet;

the purification area is an adsorption column 3 and an adsorption column 4, circulating liquid is driven by a circulating pump to enter the adsorption column 3 and the adsorption column 4, and target product components adsorbed in the previous period are purified;

the desorption area is an adsorption column 1 and an adsorption column 2, a desorbent pump drives the desorbent and part of the desorbent from the buffer area to enter the adsorption column 1 and the adsorption column 2, the target product components purified in the previous period are eluted, and the target product components are pumped out of the system to achieve the purpose of adsorption separation;

the buffer area is an adsorption column 7 and an adsorption column 8, most of target product components in the raw materials are adsorbed in the adsorption area, and the mixed liquid of a large amount of non-target components and a small amount of target components is left to enter the buffer area to wait for the next period;

the valves are controlled to be switched to change the positions of feeding and discharging in time sequences of t-2t, 2t-3t and 3t-4t, so that the simulated movement of the adsorption area, the purification area, the desorption area and the buffer area is realized.

Advantageous effects

(1) Compared with off-line detection, the on-line mid-infrared spectrum detection system is more convenient and the accuracy of the measurement result is credible; the operation condition of the adsorption process is adjusted in real time according to the online detection result, so that the quick response of the process operation is realized, and the production efficiency, the product quality and the product percent of pass are improved. The infrared spectrum range is selected, the anti-interference capability is strong, the measurement precision is high, the product quality control in industrial mass production is well realized, the cost is reduced, and the operation is convenient.

(2) The adsorption separation process operation can be monitored in real time by arranging an on-line mid-infrared spectrum detection system in the adsorption device. Furthermore, all set up online mid infrared spectrum detecting system on the import of every adsorption column and outlet pipeline, can improve the control precision, realize the real time monitoring to every adsorption column operating condition and performance, and then adjust the operating condition of corresponding adsorption column, the maximize improves production efficiency, reduces cost and energy consumption to the time that the adsorption column needs to be changed is reminded to the accuracy.

(3) The branch sample cell combines the measurement of fiber probe, has reduced sample measurement pretreatment process, reduces the loaded down with trivial details process of detection, realizes on-line measuring. The detection method is easy to realize, has wide requirements on environmental conditions, and is suitable for detecting the olefin, the alkane and the alkyne in the hydrocarbons which are liquid at the temperature of between 80 ℃ below zero and 200 ℃ and under the pressure of 69 bar. The detection has no damage to the sample, other auxiliary reagents are not required to be added, the detection difficulty is reduced, the detection frequency is improved, and timely data guidance is provided for process operation. The detection carbon number is C4-C40, and the range is wider.

(4) The program control valve group is adopted to replace the traditional multi-channel rotary valve to control the cycle switching of the simulated moving bed, so that the equipment cost is reduced; the program control valve group can be flexibly cut out according to the maintenance requirement, so that the equipment maintenance is facilitated; each adsorption column can be cut out for maintenance, and the system is cut in after the adsorbent is replaced, so that the long-period running capacity of the device is greatly improved. Meanwhile, the volumes of all pipelines connected with the adsorption column are the same, and the relative position of the circulating pump in the area is unchanged, so that the flow of the circulating pump is unchanged, the pressure fluctuation is small, and the control is simple.

Drawings

FIG. 1 is a schematic view of the detection of a sample according to the present invention

Figure 2 is a schematic diagram of a high efficiency simulated moving bed apparatus of the present invention.

Detailed Description

The schematic diagram of the sample detection of the present invention is shown in FIG. 1. And a branch with a test sample pool is arranged on the material pipeline, and an online mid-infrared spectrometer is adopted to detect the material in the sample pool.

The detection steps are as follows:

(1) calibration model establishment

Determining the contents of olefin, alkane and alkyne in 100 Fischer-Tropsch synthesis oil samples by adopting a gas chromatography; and then, performing mid-infrared spectrum scanning on each sample through a sample cell, and selecting C-C bond at 3100-3010 cm^-1Is a characteristic spectral region; the C-C bond is 2975-2800 cm^-1Is a characteristic spectral region; the C ≡ C bond is 3300-2150 cm^-1Relating the response value of the characteristic spectrum region with the contents of alkene, alkane and alkyne of a sample determined by adopting a gas chromatography, and respectively establishing a correction model by adopting a least square method of a stoichiometric method;

the sample enters a sample cell from an inlet pipe after passing through a material pipeline, the inlet pipe and an outlet pipe which enter a test sample cell are respectively led out from the front and the back of a regulating valve with pressure difference in the material pipeline, the pressure in the sample cell is regulated to be below 69bar through a valve, the temperature of the material entering the sample cell is not higher than 200 ℃, the sample cell is a branch flow sample cell, and an infrared spectrometer adopts an optical fiber probe type measurement.

The gas chromatograph is Agilent 7820 gas chromatograph, PONA chromatographic column, split/non-split sample inlet, and PONA chromatographic column.

The used mid-infrared spectrometer is a Metler ReactrI 15, and the spectral range is 4000-650cm^-1Resolution of 4cm^-1。

And performing spectral scanning through the optical fiber probe, and processing through an instrument software workstation to obtain the spectral peak height under the characteristic wavelength.

(2) Determination of content

Performing mid-infrared spectrum scanning on the sample under the same test condition as that of the calibration model, wherein the mid-infrared spectrum scanning is respectively 3100-3010 cm^-1、2975～2800cm^-1、3300～2150cm^-1And substituting the response values of the spectral regions into the corresponding correction models to obtain the contents of the alkene, the alkane and the alkyne in the sample. The detection result of the gas chromatography of the sample is compared with the detection result of the on-line mid-infrared spectroscopy, so that the detection results of the on-line mid-infrared spectroscopy and the gas chromatography are basically consistent, and the infrared spectroscopy measures the junction compared with the gas chromatographyThe maximum fruit deviation is only about +/-2%.

In the adsorption and separation process of the adsorption device, the adsorption and separation process can be monitored in real time through an online mid-infrared spectrum detection system arranged in the adsorption device so as to adjust the operation condition or maintain and replace the adsorption column.

Fig. 2 specifically shows the structure of a simulated moving bed apparatus according to the present invention, taking an adsorption bed comprising 8 adsorption columns as an example.

A high-efficiency simulated moving bed device comprises an adsorption bed, a raw material feeding system, a desorbent feeding system, a circulating system, a liquid pumping system, a residual liquid pumping system, a program control valve group and an automatic control system; wherein, the adsorption beds are divided into an adsorption zone, a purification zone, a desorption zone and a buffer zone (it should be noted that the present embodiment adopts an adsorption bed comprising an adsorption zone, a purification zone, a desorption zone and a buffer zone, but the buffer zone is not necessarily selected for the present invention, and is optional);

raw material feed valves A3, B3, C3, D3, E3, F3, G3 and H3, desorbent feed valves A2, B2, C2, D2, E2, F2, G2 and H2, circulating liquid feed valves A4, B4, C4, D4, E4, F4, G4 and H4 are respectively arranged at the upper ends of the adsorption columns 1 to 8;

the lower ends of the adsorption columns 1 to 8 are respectively provided with raffinate discharge valves A5, B5, C5, D5, E5, F5, G5 and H5, and extract discharge valves A6, B6, C6, D6, E6, F6, G6 and H6;

one-way valves A1, B1, C1, D1, E1, F1, G1 and H1 are arranged between two adjacent adsorption columns;

the raw material feeding system is connected with raw material feeding valves A3, B3, C3, D3, E3, F3, G3 and H3 of each adsorption column;

the desorbent feed system is connected with desorbent feed valves A2, B2, C2, D2, E2, F2, G2 and H2 of each adsorption column;

the circulating system comprises a circulating pump, and the circulating liquid feeding system is connected with circulating liquid feeding valves A4, B4, C4, D4, E4, F4, G4 and H4 of each adsorption column through the circulating pump;

the extract system is connected with extract discharge valves A6, B6, C6, D6, E6, F6, G6 and H6 of each adsorption column;

the raffinate system is connected with raffinate discharge valves A5, B5, C5, D5, E5, F5, G5 and H5 of each adsorption column;

in this embodiment, the relative position of the circulating pump in the region is unchanged, so the flow rate of the circulating pump is unchanged, the volume of the connecting pipeline between each adsorption column is the same, and the volume of the pipeline connecting each adsorption column to the circulating pump is the same. Therefore, the circulation pump of the embodiment has the advantages of unchanged flow rate, small pressure fluctuation and simple control.

In this embodiment, all the valves constitute a program control valve group, the program control valve group is connected with an automatic control system, and the automatic control system can control the opening and closing states of each valve in the program control valve group.

As a modification of this embodiment, optionally, the raw material feeding system includes a raw material pump and a raw material heater located downstream of the raw material pump, and an outlet pipeline of the raw material heater is connected to the adsorption column; the raw material pump can provide feeding power for the raw material feeding, and the raw material heater can heat the raw material to suitable problem, improves the adsorption activity, and specific pumping pressure and heating temperature are decided according to the characteristics of thing separation system.

As a modification of this embodiment, the desorbent feed system may optionally include a desorbent pump and a desorbent heater located downstream of the desorbent pump, the desorbent heater outlet line being connected to the adsorption column; the desorbent pump can provide feeding power for the desorbent feeding, and the desorbent heater can heat the desorbent to a proper temperature to improve the desorption capacity, and the specific pumping pressure and the heating temperature are determined according to the characteristics of the substance separation system.

As a modification of this embodiment, the extract system may optionally include an extract pump, and the extract pump is connected to the extract line of the adsorbent bed. The liquid pumping pump provides pumping power for the pumped liquid.

As a modification of this embodiment, the raffinate system may optionally include a raffinate pump connected to the raffinate line of the adsorbent bed. The raffinate pump provides the raffinate pumping power.

As an improvement of this embodiment, optionally, a feed inlet of the circulation pump of the circulation system is connected to an extract liquid line of the adsorption bed; and circulating the extract.

As a modification of the present embodiment, it is possible, alternatively,

the valve types in the program control valve group are respectively and independently selected to be one of a ball valve, a needle valve, a stop valve and a butterfly valve; that is, the 56 valves of the present embodiment are each independently one of a ball valve, a needle valve, a stop valve, and a butterfly valve, and do not interfere with each other. The valve actuating mechanism is pneumatic or electric.

As a modification of this embodiment, the relative position of the circulating pump in the zone is optionally constant, so that the flow rate of the circulating pump is constant, the volume of the connecting line between each adsorption column is the same, and the volume of the connecting line between each adsorption column and the circulating pump is the same. Therefore, the circulation pump of the embodiment has the advantages of unchanged flow rate, small pressure fluctuation and simple control.