CN111569800A - System applied to real-time reaction state monitoring of heavy oil processing industrial reactor - Google Patents
System applied to real-time reaction state monitoring of heavy oil processing industrial reactor Download PDFInfo
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 53
- 238000012545 processing Methods 0.000 title claims abstract description 47
- 239000000295 fuel oil Substances 0.000 title claims abstract description 33
- 238000012544 monitoring process Methods 0.000 title claims abstract description 14
- 238000004458 analytical method Methods 0.000 claims abstract description 33
- 238000009529 body temperature measurement Methods 0.000 claims abstract description 26
- 238000010438 heat treatment Methods 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 13
- 230000017525 heat dissipation Effects 0.000 claims description 9
- 239000003921 oil Substances 0.000 claims description 9
- 239000000463 material Substances 0.000 claims description 8
- 238000004364 calculation method Methods 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 230000010354 integration Effects 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 230000005540 biological transmission Effects 0.000 claims description 2
- 230000000694 effects Effects 0.000 description 5
- 238000005984 hydrogenation reaction Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 238000004939 coking Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000011020 pilot scale process Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
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- B01J19/0006—Controlling or regulating processes
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- G05B19/41875—Total factory control, i.e. centrally controlling a plurality of machines, e.g. direct or distributed numerical control [DNC], flexible manufacturing systems [FMS], integrated manufacturing systems [IMS] or computer integrated manufacturing [CIM] characterised by quality surveillance of production
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- B01J2219/00054—Controlling or regulating the heat exchange system
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- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
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Abstract
The invention discloses a system for monitoring a real-time reaction state of a reactor in heavy oil processing industry, which specifically comprises four modules: the reactor central temperature measurement module, the outer wall temperature measurement module, the specific heat analysis module, the data processing module and the display module obtain a model curve through program calculation for each temperature measurement point inside and outside the reaction system, and finally the reaction state inside the reactor can be monitored in real time through the change of the model curve. The invention has the advantages of convenient operation, strong real-time performance, accurate pointing and strong anti-interference capability.
Description
Technical Field
The invention relates to the technical field of chemical engineering, in particular to a system for monitoring the real-time reaction state of a reactor in the heavy oil processing industry.
Background
Statistics in recent years show that the proportion of light crude oil is reduced year by year in the petroleum recoverable reserves which are mainly heavy oil and medium oil. In the future, the newly added crude oil supply mainly comprises heavy and inferior oil, and the heavy and inferior trends of crude oil resources are obvious. With the gradual deepening of the trend, the current heavy oil processing technology becomes a key point for research and development and receives wide attention.
Due to the characteristic of difficult processing of heavy oil, the processing technology of heavy oil is usually higher in temperature and pressure, and the corresponding heavy and inferior oil raw materials usually have very large coking tendency, namely extremely high colloid asphaltene content and carbon residue value, which brings great safety risk and unstable factors to a reaction process system, so that effective real-time monitoring of the real reaction state in the reactor is necessary.
The heavy and inferior oil conversion reaction for the light conversion of heavy and inferior oil has complex structure, the cracking, hydrocracking, hydrogenation reaction and the like have very obvious heat effects, the heat effect in the coking stage and the heat effect in the hydrogenation state have very obvious difference, the difference of heat absorption and release can be caused due to the difference of hydrogenation depth in the stable reaction stage, and the stability and the conversion efficiency of the reaction system can be effectively controlled and predicted by utilizing the heat effect of the reaction system to carry out real-time monitoring on the reaction system.
Chinese patent (CN110314634A) discloses a method for real-time monitoring of internal reaction state of a tubular reactor, which measures internal and external temperature measurement points and output power of the reactor through an integrated system of five modules (a reactor center temperature measurement module, an outer wall temperature measurement module, a specific heat analysis module, a data processing module, and a display module), calculates a model curve through a predetermined program, and can real-time monitor internal reaction state of the reactor according to the change of the model curve. However, the method of the invention necessarily needs to provide the output power of the heating part of the reactor, and for most industrial reactors, the reactor is not provided with an electric heating system, does not have the basic conditions necessary for the method, and cannot provide the parameters required for the calculation of the invention.
For a general industrial reactor for processing heavy oil, an operation mode that raw materials are preheated and enter the similar adiabatic reactor for reaction is adopted, compared with a pilot-scale reaction, the imbalance of reaction temperature causes more complex reaction working conditions, the reaction risk is correspondingly increased, and monitoring of an internal reaction state is more necessary, so that a new method is needed for analog calculation of an exothermic curve of an industrial reaction system.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide a system applied to monitoring the real-time reaction state of a heavy oil processing industrial reactor, which can evaluate the internal reaction state and effect of the heavy oil processing industrial reactor in real time.
In order to achieve the purpose, the invention adopts the technical scheme that:
the utility model provides a be applied to real-time reaction state monitoring's of heavy oil processing industry reactor system, is including lieing in the inside industry reactor center temperature measurement module of heavy oil processing industry reactor shell, sets up the industry reactor shell temperature measurement module in the heavy oil processing industry reactor shell outside, industry reactor center temperature measurement module and industry reactor shell temperature measurement module be used for transmitting measured real-time data to data processing module, show through display module, heavy oil processing industry reactor shell top and bottom be provided with specific heat analysis module respectively, specific heat analysis module off-line or the transmission of on-line analysis gained data to data processing module.
The central temperature measuring module of the industrial reactor is a plurality of thermocouples extending into the reactor tube, and L temperature measuring points are distributed from top to bottom, wherein L is more than or equal to 4.
The industrial reactor shell temperature measurement module is a reactor heating jacket distributed on a heavy oil processing industrial reactor shell, L temperature measurement points are arranged on the outer wall of the reactor heating jacket, the L temperature measurement points correspond to the internal temperature measurement points, the total number of the L temperature measurement points is L, and L is more than or equal to 4.
The data processing module is a device for integrating the measured data of each measuring point, performing integration processing and integrating in real time.
The material specific heat analysis module can input specific heat data of oil products at the inlet end and the outlet end of the reactor into the data processing module for subsequent analysis by an off-line or on-line method.
The data processing module can adopt the following formula to program a data processing program at the nth temperature measuring point on the main body of the industrial reactor:
QR－QA－QE＝CnvtTn－Cn-1vtTn-1
wherein QRFor the reaction exotherm (kJ), QATo react endotherms (kJ), QEFor convective heat dissipation (kJ), CnThe constant pressure heat capacity (kJ. kg) of heavy oil material flowing through the nth temperature measuring point-1K-1) V is the raw material feed rate (kg. h)-1) T is the reaction time (h), TnThe temperature (K) at the nth temperature measuring point of the reaction center;
the reaction exotherm and the reaction endotherm are defined as Q as the net reaction exotherm, and Q is equal to QR－QA。
The convection heat dissipation is calculated by adopting the following formula:
QE＝αTF(TW,n－TS)t
αT＝33.5+0.21TW,n
α thereinTFor the heat dissipation coefficient (kJ.m) of the outer surface of the heating jacket-2h-1K-1) And F is the external surface area (m) of the reactor at the corresponding temperature measuring point2)，TW，nFor heating the outer surface temperature (K), T of the jacketSIs the ambient temperature (K) and t is the time (h);
when heavy oil flows through the nth temperature measuring point at the reaction time t, the net exothermic quantity Q of the reaction at the pointnComprises the following steps:
Qn＝CnvtTn-Cn-1vtTn-1+(33.5+0.21TW，n)F(TW，n-TS)t
namely:
Qn＝(CnvtTn)′+(33.5+0.21TW，n)F(TW，n-TS)t
＝Cnvt(Tn)′+(Cn)′vtTn+(33.5+0.21TW，n)F(TW，n-TS)t
for an arbitrarily selected time period t2-t1Definition of fn(t) represents a continuous function of the temperature at the nth temperature measurement point as a function of time t;
the heat capacity data and the heat capacity derivative data are provided by the analysis of the specific heat analysis module, and the result of the specific heat analysis of the reactor inlet is recorded as CinThe specific heat analysis result of the outlet of the reactor is Cout；
Then:
Cn＝Cin+R(n)/L
r (n) in the formula for specific heat change as described above, which is related to material properties, can be obtained by off-line analysis, and has:
CL＝Cout
the preparation method is easy to obtain,
(Cn)′＝R′(n)/L
defining net heat release per unit time
Will Tn、(Tn)’、Cn、(Cn) ' substitution of QnThe calculation formula is as follows:
the method finally comprises the following steps:
said time period t2-t1And can be 1s-6 h.
The invention has the beneficial effects that:
the invention obtains the model curve through program calculation, and finally can monitor the reaction state in the reactor in real time through the change of the model curve. The invention has the advantages of convenient operation, strong real-time performance, accurate pointing and strong anti-interference capability.
Drawings
Fig. 1 is a simplified flow diagram of the present patent.
Wherein 1, a heavy oil processing industrial reactor shell; 2. a central temperature measuring module of the industrial reactor; 3. a temperature measuring module of the industrial reactor shell; 4. a material specific heat analysis module; 5. a data processing module; 6. and a display module.
FIG. 2 is a graph of the reaction conditions over time calculated according to the method of the present invention under different reaction steady state conditions.
Detailed Description
The present invention will be described in further detail with reference to the accompanying drawings.
As shown in fig. 1: the real-time monitoring system mainly comprises the following parts: reactor center temperature measurement module, outer wall temperature measurement module, specific heat analysis module, data processing module and display module. The data processing module receives real-time data measured by the central temperature measuring module and the outer wall temperature measuring module of the heavy oil processing industrial reactor, combines the data obtained by the off-line or on-line analysis of the specific heat analysis module, calculates by a preset calculation method to obtain a state curve, displays the state curve on the display module, and can monitor and evaluate the reaction state in the heavy oil processing industrial reactor in real time through the state curve.
The real-time monitoring system may be an independent system, or may be included in the entire DCS control system of the reaction process.
The heavy oil processing industrial reactor as described above may be a bubbling bed, slurry bed, ebullating bed or the like reactor.
The reactor central temperature measuring module is a plurality of thermocouples extending into the reactor tube, wherein L temperature measuring points are distributed from top to bottom, L is not less than 4, and can be increased according to actual conditions.
The outer wall temperature measuring module is a plurality of temperature measuring points distributed on the outer wall of the reactor heating jacket, and L temperature measuring points are counted corresponding to the inner temperature measuring points, wherein L is more than or equal to 4.
The data processing module is a device for integrating the measured data of each measuring point, performing integration processing and integrating in real time.
The specific heat analysis module can input specific heat data of oil products at the inlet end and the outlet end of the reactor into the data processing module for subsequent analysis by an off-line or on-line method.
As for the data processing module, the data processing program can be programmed at the nth temperature measuring point in the heating module by using the following formula:
QR－QA－QE＝CnvtTn－Cn-1vtTn-1
wherein QRFor the reaction exotherm (kJ), QATo react endotherms (kJ), QEFor convective heat dissipation (kJ), CnThe constant pressure heat capacity (kJ. kg) of heavy oil material flowing through the nth temperature measuring point-1K-1) V is the raw material feed rate (kg. h)-1) T is the reaction time (h), TnThe temperature (K) at the nth temperature measurement point of the reaction center.
The reaction exotherm and the endothermic heat of reaction are as described above, and Q is defined as the net exotherm of the reaction, and Q is equal to QR－QA。
The convection heat dissipation as described above is calculated using the following formula:
QE＝αTF(TW,n－TS)t
αT＝33.5+0.21TW,n
α thereinTFor the heat dissipation coefficient (kJ.m) of the outer surface of the heating jacket-2h-1K-1) And F is the external surface area (m) of the reactor at the corresponding temperature measuring point2)，TW，nFor heating the outer surface temperature (K), T of the jacketSIs the ambient temperature (K) and t is the time (h).
As described above, when the heavy oil passes through the nth temperature measurement point at the reaction time t, the net exotherm Q of the reaction at that pointnComprises the following steps:
Qn＝CnvtTn-Cn-1vtTn-1+(33.5+0.21TW，n)F(TW，n-TS)t
namely:
Qn＝(CnvtTn)′+(33.5+0.21Tw，n)F(TW，n-TS)t
＝Cnvt(Tn)′+(Cn)′vtTn+(33.5+0.21TW，n)F(TW，n-TS)t
for an arbitrarily selected time period t2-t1Definition of fn(t) represents a continuous function of the temperature at the nth temperature measurement point as a function of time t.
The heat capacity data and the heat capacity derivative data are provided by the analysis of the specific heat analysis module, and the result of the specific heat analysis of the reactor inlet is recorded as CinThe specific heat analysis result of the outlet of the reactor is Cout。
Then:
Cn＝Cin+R(n)/L
r (n) in the specific heat change formula is related to material properties and can be obtained by off-line analysis. And has the following components:
CL＝Cout
the preparation method is easy to obtain,
(Cn)′＝R′(n)/L
defining net heat release per unit time
Will Tn、(Tn)’、Cn、(Cn) ' substitution of QnThe calculation formula is as follows:
the method finally comprises the following steps:
the time period t as described above2-t1And can be 1s-6 h.
As described above, it is easy to obtain,
is the total exotherm from the start of the reaction to time t.
Q is as described above and
the absolute values of the positive values respectively represent the net heat release and the net heat release per unit time, and the absolute values of the negative values respectively represent the net heat absorption and the net heat absorption per unit time.
The display module is a display or a display screen for displaying the real-time result of the data processing module.
The method of the state curve displayed by the display to the reaction state inside the reactor will be described in detail by examples.
As shown in fig. 2: taking a heavy oil hydrogenation device of 100 ten thousand tons/year as an example, the reactor is a three-stage reactor connected in series. The specific properties of the FCC slurry oil as the reaction raw material are shown in the table I. The reaction temperature is 460 ℃, the exothermic curves obtained by calculation under the conditions of 1 percent, 0.75 percent and 0.5 percent of the catalysts in examples 1, 2 and 3 respectively show uniform change rules, and the differences in details can be seen from the second graph, so that a change mode is generally reflected and can be used as an indication of the real-time reaction state in the reactor in the heavy oil processing industry.
Table one Properties of the raw materials
The foregoing is illustrative of the preferred embodiment of the present invention and is not to be construed as limiting thereof in any way, the scope of the invention being indicated in the claims, and any changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Claims (7)
1. The utility model provides a be applied to real-time reaction state monitoring's of heavy oil processing industry reactor system which characterized in that, is including the industrial reactor center temperature measurement module that is located heavy oil processing industry reactor shell inside, sets up the industrial reactor shell temperature measurement module in the heavy oil processing industry reactor shell outside, industrial reactor center temperature measurement module and industrial reactor shell temperature measurement module be used for transmitting measured real-time data to data processing module, show through the display module, heavy oil processing industry reactor shell top and bottom be provided with specific heat analysis module respectively, specific heat analysis module off-line or on-line analysis gained data transmission to data processing module.
2. The system of claim 1, wherein the central temperature measuring module of the industrial reactor is a plurality of thermocouples extending into the reactor tube, and L temperature measuring points are distributed from top to bottom, wherein L is greater than or equal to 4.
3. The system of claim 1, wherein the temperature measuring module of the industrial reactor shell is a reactor heating jacket distributed on the industrial reactor shell, and L temperature measuring points are arranged on the outer wall of the reactor heating jacket, corresponding to the internal temperature measuring points, for a total of L temperature measuring points, where L is greater than or equal to 4.
4. The system as claimed in claim 1, wherein the data processing module is a device for integrating the measured data of the measuring points and performing the integration and the real-time integration.
5. The system of claim 1, wherein the specific heat analysis module is configured to input specific heat data of the oil at the inlet and outlet ends of the reactor into the data processing module for subsequent analysis by an off-line or on-line method.
6. The system of claim 1, wherein the data processing module is programmed to perform a data processing procedure for the nth temperature measuring point in the main body of the industrial reactor according to the following formula:
QR－QA－QE＝CnvtTn－Cn-1vtTn-1
wherein QRFor the reaction exotherm (kJ), QATo react endotherms (kJ), QEFor convective heat dissipation (kJ), CnThe constant pressure heat capacity (kJ. kg) of heavy oil material flowing through the nth temperature measuring point-1K-1) V is the raw material feed rate (kg. h)-1) T is the reaction time (h), TnTo reactThe temperature (K) at the central nth temperature measuring point;
the reaction exotherm and the reaction endotherm are defined as Q as the net reaction exotherm, and Q is equal to QR－QA。
The convection heat dissipation is calculated by adopting the following formula:
QE＝αTF(TW,n－TS)t
αT＝33.5+0.21TW,n
α thereinTFor the heat dissipation coefficient (kJ.m) of the outer surface of the heating jacket-2h-1K-1) And F is the external surface area (m) of the reactor at the corresponding temperature measuring point2)，TW，nFor heating the outer surface temperature (K), T of the jacketSIs the ambient temperature (K) and t is the time (h);
when heavy oil flows through the nth temperature measuring point at the reaction time t, the net exothermic quantity Q of the reaction at the pointnComprises the following steps:
Qn＝CnvtTn-Cn-1vtTn-1+(33.5+0.21TW，n)F(TW，n-TS)t
namely:
Qn＝(CnvtTn)′+(33.5+0.21TW，n)F(TW，n-TS)t
＝Cnvt(Tn)′+(Cn)′vtTn+(33.5+0.21TW，n)F(TW，n-TS)t
for an arbitrarily selected time period t2-t1Definition of fn(t) represents a continuous function of the temperature at the nth temperature measurement point as a function of time t;
heat capacity data and heat capacity derivative data as described aboveThe specific heat is provided by analysis of a specific heat analysis module, and the specific heat result of the analysis of the inlet of the reactor is recorded as CinThe specific heat analysis result of the outlet of the reactor is Cout；
Then:
Cn＝Cin+R(n)/L
r (n) in the formula for specific heat change as described above, which is related to material properties, can be obtained by off-line analysis, and has:
CL＝Cout
the preparation method is easy to obtain,
(Cn)′＝R′(n)/L
defining net heat release per unit time
Will Tn、(Tn)’、Cn、(Cn) ' substitution of QnThe calculation formula is as follows:
the method finally comprises the following steps:
7. the system for real-time reaction status monitoring of heavy oil processing industrial reactor as claimed in claim 6, wherein the time period t is set as2-t1And can be 1s-6 h.
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