CN109143984B - Multi-level control device and method for preventing shift reactor from temperature runaway - Google Patents
Multi-level control device and method for preventing shift reactor from temperature runaway Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 16
- 230000001105 regulatory effect Effects 0.000 claims description 62
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 59
- 229910052760 oxygen Inorganic materials 0.000 claims description 49
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 48
- 239000001301 oxygen Substances 0.000 claims description 48
- 229910052757 nitrogen Inorganic materials 0.000 claims description 29
- 239000007789 gas Substances 0.000 claims description 25
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 19
- 238000000926 separation method Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- 238000012544 monitoring process Methods 0.000 claims description 6
- 230000000694 effects Effects 0.000 abstract description 5
- 230000033228 biological regulation Effects 0.000 abstract description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 6
- 230000009466 transformation Effects 0.000 description 6
- 238000007086 side reaction Methods 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000014759 maintenance of location Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 238000011282 treatment Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000004880 explosion Methods 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
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- 238000006467 substitution reaction Methods 0.000 description 1
- 238000011269 treatment regimen Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- G—PHYSICS
- G05—CONTROLLING; REGULATING
- G05B—CONTROL OR REGULATING SYSTEMS IN GENERAL; FUNCTIONAL ELEMENTS OF SUCH SYSTEMS; MONITORING OR TESTING ARRANGEMENTS FOR SUCH SYSTEMS OR ELEMENTS
- G05B19/00—Programme-control systems
- G05B19/02—Programme-control systems electric
- G05B19/418—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]
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
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- G—PHYSICS
- G05—CONTROLLING; REGULATING
- G05D—SYSTEMS FOR CONTROLLING OR REGULATING NON-ELECTRIC VARIABLES
- G05D27/00—Simultaneous control of variables covered by two or more of main groups G05D1/00 - G05D25/00
- G05D27/02—Simultaneous control of variables covered by two or more of main groups G05D1/00 - G05D25/00 characterised by the use of electric means
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- G—PHYSICS
- G05—CONTROLLING; REGULATING
- G05B—CONTROL OR REGULATING SYSTEMS IN GENERAL; FUNCTIONAL ELEMENTS OF SUCH SYSTEMS; MONITORING OR TESTING ARRANGEMENTS FOR SUCH SYSTEMS OR ELEMENTS
- G05B2219/00—Program-control systems
- G05B2219/20—Pc systems
- G05B2219/25—Pc structure of the system
- G05B2219/25232—DCS, distributed control system, decentralised control unit
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Abstract
The invention belongs to the technical field of control or regulation systems, and discloses a multi-level control device and a method for preventing temperature runaway of a shift reactor. The technical scheme provides an automatic control method, so that the hysteresis effect of the operation of workers is avoided, and the accidents caused by the temperature runaway of the shift reactor are effectively avoided.
Description
Technical Field
The invention belongs to the technical field of control or regulation systems, and particularly relates to a multi-level control device and method for preventing temperature runaway of a shift reactor.
Background
The principle of CO transformation is that CO and water vapor in gas are subjected to transformation reaction under the action of transformation catalyst under the condition of certain temperature and pressure to generate H2And CO2. The reaction formula is as follows: CO + H2O＝CO2＋H2＋41.2 kJ/mol
When the water/gas ratio is low, methanation side reaction occurs, and when the oxygen content is higher, oxidation side reaction occurs, and the reaction heat of the two reactions is far higher than that of the CO shift reaction. Therefore, if methanation or oxidation side reactions occur in the shift reactor, the shift reactor temperature will rise rapidly, if so, the catalyst activity will be reduced, if so, the catalyst will be burned out, the shift reactor and internals will be damaged, and even explosion will occur.
To avoid the risk of runaway in shift reactors, the usual measures are: adding nitrogen in emergency, opening pressure regulating valves before and after the shift reactor to release air and reduce pressure, lowering the inlet temperature of the shift reactor, raising the water/gas ratio, lowering CO content, raising airspeed, etc. The safety measures for preventing temperature runaway of the CO shift reactor at present have the following problems: 1. aiming at the danger of the temperature runaway of the shift reactor, an automatic control system is not provided, the shift reactor is mostly processed manually by workers, the reaction is delayed, and the possibility of misoperation is high; 2. there is no quantitative control index for the danger of shift reactor runaway. If the treatment and control are carried out by relying on experience and manual operation, the temperature runaway accident of the shift reactor is still difficult to avoid and control. Therefore, it is desirable to provide a control method that prevents shift reactor runaway.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention is realized by adopting the following technical scheme:
a multi-level control device and a method for preventing temperature runaway of a shift reactor comprise a gas-liquid separator, a heat exchanger connected with the gas-liquid separator, a shift reactor connected with the heat exchanger, a temperature regulating valve, a pressure regulating valve of an unconverted system, a pressure regulating valve of a converted system, a nitrogen feeding regulating valve, an oxygen content monitor, a temperature monitor and a gas-liquid separation and steam generation device, wherein the temperature regulating valve is arranged on a short connecting pipeline of the heat exchanger, an accident nitrogen line is arranged on an inlet pipeline of the shift reactor, the nitrogen line is provided with the nitrogen feeding regulating valve, a temperature monitor is arranged at an outlet of the shift reactor, and the oxygen content monitor is arranged on a pipeline before synthesis gas enters the shift reactor.
A gas-liquid separation and steam generation device is arranged at the inlet of the heat exchanger, and a pressure regulating valve of an unconverted system is arranged at the outlet of the device; and a gas-liquid separation and steam generation device is arranged at the outlet of the heat exchanger, and a pressure regulating valve of a conversion system is arranged at the outlet of the device.
The oxygen content monitor is arranged in front of the gas separator.
The temperature monitor and the oxygen content monitor contain alarm devices, and alarm can be given out when the temperature monitor and the oxygen content monitor exceed set values.
The monitoring mechanism is an oxygen content monitor and a temperature monitor, wherein the oxygen content monitor is arranged on a pipeline before the synthesis gas enters the shift reactor and can be arranged in front of and behind the gas-liquid separator, and the temperature monitor is arranged in front of an outlet of the shift reactor and the heat exchanger. The actuating mechanism comprises a temperature regulating valve in front of the shift reactor, a pressure regulating valve of a non-shift system, a pressure regulating valve of a shift system, a nitrogen feeding regulating valve and the like, wherein the temperature regulating valve is installed on a short connecting pipeline of the heat exchanger, the feeding temperature is reduced by increasing the opening degree of the regulating valve, an accident nitrogen line is communicated on a feeding pipeline of the shift reactor, and the nitrogen feeding regulating valve is arranged on the accident nitrogen line. The control system is mainly a Distributed Control System (DCS).
A multi-level control method for preventing shift reactor runaway comprising the steps of:
(1) monitoring the temperature and oxygen content of the synthesis gas, and setting a three-level alarm value;
(2) when a first-level alarm occurs, the opening degree of the temperature regulating valve is increased;
when a secondary alarm occurs, increasing the opening degrees of the pressure regulating valve of the unconverted system and the pressure regulating valve of the converted system;
and when a three-level alarm occurs, opening the nitrogen feeding regulating valve.
The first-level alarm is a high-temperature alarm or a high-oxygen-content alarm, the second-level alarm is a high-temperature alarm or a high-oxygen-content alarm, and the third-level alarm is a high-temperature interlock or a high-oxygen-content interlock. The temperature high alarm is set to a certain value between 420 and 450 ℃, the oxygen content high alarm is set to a certain value between 0.1 and 0.24 percent v/v, and the opening degree of the temperature regulating valve is increased when the temperature high alarm or the oxygen content high alarm is carried out; the temperature high-high alarm is set to a certain value between 440 ℃ and 470 ℃, the oxygen content high-high alarm is set to a certain value between 0.15% v/v and 0.36% v/v, and when the temperature high-high alarm or the oxygen content high-high alarm is carried out, the opening degrees of the pressure regulating valve of the untransformed system and the pressure regulating valve of the transformed system are increased; the temperature high interlock value is set at a value between 460 ℃ and 490 ℃ and the oxygen high interlock value is set at a value between 0.2 and 0.48% v/v, and the nitrogen feed adjustment valve is opened when the temperature high interlock or the oxygen high interlock is present.
The technical scheme provides an automatic control method, so that the hysteresis effect of the operation of workers is avoided; quantitative boundary conditions of alarm and interlocking are provided; a complete multi-level control system is formed, and a plurality of processing means are adopted to effectively control various deviations; effectively avoiding accidents caused by temperature runaway of the shift reactor.
Drawings
FIG. 1: the invention discloses a structural schematic diagram of a multi-level control device for preventing the temperature runaway of a shift reactor.
Wherein: 1. synthesis gas; 2. a gas-liquid separator; 3. an oxygen content monitor; 4. a gas-liquid separation and steam generation device; 5. a non-shifting system pressure regulating valve; 6. a torch; 7. a downstream process; 8. a heat exchanger; 9. a temperature regulating valve; 10. a shift system pressure regulating valve; 11. a nitrogen feed regulating valve; 12. nitrogen gas; a CO shift reactor; 14. a temperature monitor.
Detailed Description
The technical solution of the present invention will be described in further detail with reference to the accompanying drawings and the detailed description.
A multi-level control device and a method for preventing temperature runaway of a shift reactor comprise a gas-liquid separator, a heat exchanger connected with the gas-liquid separator, a shift reactor connected with the heat exchanger, a temperature regulating valve, a pressure regulating valve of an unconverted system, a pressure regulating valve of a converted system, a nitrogen feeding regulating valve, an oxygen content monitor, a temperature monitor and a gas-liquid separation and steam generation device, wherein the temperature regulating valve is arranged on a short connecting pipeline of the heat exchanger, an accident nitrogen line is arranged on an inlet pipeline of the shift reactor, the nitrogen line is provided with the nitrogen feeding regulating valve, a temperature monitor is arranged at an outlet of the shift reactor, and the oxygen content monitor is arranged on a pipeline before synthesis gas enters the shift reactor. A gas-liquid separation and steam generation device is arranged at the inlet of the heat exchanger, and a pressure regulating valve of an unconverted system is arranged at the outlet of the device; and a gas-liquid separation and steam generation device is arranged at the outlet of the heat exchanger, and a pressure regulating valve of a conversion system is arranged at the outlet of the device. The oxygen content monitor is arranged in front of the gas separator. The temperature monitor and the oxygen content monitor contain alarm devices, and alarm can be given out when the temperature monitor and the oxygen content monitor exceed set values.
A multi-level control method for preventing shift reactor runaway comprising the steps of:
(1) monitoring the temperature and oxygen content of the synthesis gas, and setting a three-level alarm value;
(2) when a first-level alarm occurs, the opening degree of the temperature regulating valve is increased;
when a secondary alarm occurs, increasing the opening degrees of the pressure regulating valve of the unconverted system and the pressure regulating valve of the converted system;
and when a three-level alarm occurs, opening the nitrogen feeding regulating valve.
The first-level alarm is a high-temperature alarm or a high-oxygen-content alarm, the second-level alarm is a high-temperature alarm or a high-oxygen-content alarm, and the third-level alarm is a high-temperature interlock or a high-oxygen-content interlock. The temperature high alarm is set to a certain value between 420 and 450 ℃, the oxygen content high alarm is set to a certain value between 0.1 and 0.24 percent v/v, and the opening degree of the temperature regulating valve is increased when the temperature high alarm or the oxygen content high alarm is carried out; the temperature high-high alarm is set to a certain value between 440 ℃ and 470 ℃, the oxygen content high-high alarm is set to a certain value between 0.15% v/v and 0.36% v/v, and when the temperature high-high alarm or the oxygen content high-high alarm is carried out, the opening degrees of the pressure regulating valve of the untransformed system and the pressure regulating valve of the transformed system are increased; the temperature high interlock value is set at a value between 460 ℃ and 490 ℃ and the oxygen high interlock value is set at a value between 0.2 and 0.48% v/v, and the nitrogen feed adjustment valve is opened when the temperature high interlock or the oxygen high interlock is present.
The principle of transformation is that CO and water vapor in gas are subjected to transformation reaction under the action of transformation catalyst under the condition of certain temperature and pressure to generate H2And CO2. The reaction formula is as follows: CO + H2O＝CO2＋H2＋41.2 kJ/mol
Assuming a feed water to gas ratio of 1.5, a mole fraction of CO in the dry gas of 41%, a shifted gas CO content exiting the shift reactor of 5% v/v (dry), and a constant pressure specific heat capacity of the gas of 29J/(mol.k), the heat evolved per mole of feed is:
1*40%*（41-5）%*41.2=5.93 kJ
the resulting adiabatic temperature rise was: 5930/29=204 deg.C
Thus, in a normal reaction, the temperature of the gas is increased by about 204 ℃ as it passes through the bed.
When methanation side reaction occurs, the reaction equation is:
CO + 3H2= CH4+ H2O +206.2 kJ/mol
CO2+ 4H2= CH4+2H2O + 165 kJ/mol
for the first reaction, every 1% v/v CH formed4The exotherm added per mole of feed was:
（206.2-41.2）/100=1.65 kJ
the excess temperature rise is therefore: 1650/29=57 deg.C
When an oxidation reaction occurs, the reaction equation is: CO +1/2O2= CO2+ 283 kJ/mol
For every 1% v/v increase in feed oxygen content, the exotherm increases per mole of feed: (283-41.2) 2/100=4.836kJ
The excess temperature rise is therefore: 4836/29=167 deg.C
Methanation and oxidation side reactions both lead to severe over-temperature shift reactions. And the exothermic effect of the oxidation reaction is much higher than that of the methanation reaction, and the existence of trace oxygen can cause remarkable temperature rise and possibly initiate the methanation reaction. Aiming at methanation reaction, the temperature of the shift reactor can be monitored, and effective control measures and an emergency treatment method are adopted. However, for the oxidation reaction, it must be prevented that the oxygen content of the feed material to the shift reactor is effectively monitored, preferably on the pipeline from the gasification furnace or the washing tower, and before the oxygen enters the shift reactor, nitrogen is filled for dilution, the gas flow rate is increased, the retention time of the oxygen entering the shift reactor is shortened, and the temperature runaway accident of the shift reactor is prevented.
The temperature monitoring point is arranged at the outlet of the shift reactor, and the oxygen content monitoring point is arranged on a pipeline before the synthesis gas enters the shift reactor and can be arranged in front of and behind the gas-liquid separator. The front of the shift reactor is connected with an accident nitrogen pipeline and is provided with a nitrogen feeding regulating valve. When the temperature or oxygen content is increased, there are three treatment strategies: the feeding temperature is reduced by increasing the opening of a temperature regulating valve; the gas flow rate is increased, so that the retention time in the shift reactor is shortened, and the method is realized by increasing the opening degrees of a pressure regulating valve of the non-shift system and a pressure regulating valve of the shift system; introducing accident nitrogen to dilute CO and O in the gas2Etc. and increase the gas flow rate, which is the most effective method, by opening the nitrogen feed regulating valve.
And controlling in a grading way according to different rising degrees of the temperature and the oxygen content.
A first stage: the temperature is 420-450 ℃, the rising amplitude is small, the oxygen content is 0.1-0.24% v/v, so that serious overtemperature is not caused, and the opening degree of the temperature regulating valve is increased.
And a second stage: the temperature is 440-470 ℃, the rising amplitude is moderate, and the oxygen content is 0.15-0.36% v/v, which can cause moderate temperature rise and possibly cause linked temperature-runaway effect, therefore, the opening degree of the pressure regulating valve of the non-conversion system and the opening degree of the pressure regulating valve of the conversion system need to be simultaneously increased.
And a third stage: the temperature was 460-490 ℃ at a value where the rise was severe and the oxygen content was 0.2-0.48% v/v, which can trigger severe temperature rise and required interlocking and rapid opening of the nitrogen feed adjustment valve.
The examples are merely illustrative of the technical solution of the present invention and are not intended to limit it in any way; although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions.
Claims (6)
1. A multi-stage control device for preventing shift reactor runaway, comprising: the device comprises a gas-liquid separator, a heat exchanger connected with the gas-liquid separator, a shift reactor connected with the heat exchanger, a temperature regulating valve, a system pressure regulating valve which is not shifted, a system pressure regulating valve which is shifted, a nitrogen feeding regulating valve, an oxygen content monitor, a temperature monitor and a gas-liquid separation and steam generation device, wherein the temperature regulating valve is installed on a short connecting pipeline of the heat exchanger, an accident nitrogen line is arranged on an inlet pipeline of the shift reactor, the nitrogen feeding regulating valve is arranged on the nitrogen line, the temperature monitor is arranged at the outlet of the shift reactor, and the oxygen content monitor is installed on a pipeline before synthesis gas enters the shift reactor.
2. The multi-stage control device for preventing shift reactor runaway as recited in claim 1, wherein: a gas-liquid separation and steam generation device is arranged at the inlet of the heat exchanger, and a pressure regulating valve of an unconverted system is arranged at the outlet of the device; and a gas-liquid separation and steam generation device is arranged at the outlet of the heat exchanger, and a pressure regulating valve of a conversion system is arranged at the outlet of the device.
3. The multi-stage control device for preventing shift reactor runaway as recited in claim 1, wherein: the oxygen content monitor is arranged in front of the gas separator.
4. A multi-stage control device for preventing shift reactor runaway as claimed in any one of claims 1 to 3, wherein: the temperature monitor and the oxygen content monitor contain alarm devices, and alarm can be given out when the temperature monitor and the oxygen content monitor exceed set values.
5. A multi-level control method for preventing shift reactor runaway, comprising the steps of:
(1) monitoring the temperature and oxygen content of the synthesis gas, and setting a three-level alarm value;
the first-level alarm is a high-temperature alarm or a high-oxygen-content alarm, the second-level alarm is a high-temperature alarm or a high-oxygen-content alarm, and the third-level alarm is a high-temperature interlock or a high-oxygen-content interlock;
(2) when a first-level alarm occurs, the opening degree of the temperature regulating valve is increased;
when a secondary alarm occurs, increasing the opening degrees of the pressure regulating valve of the unconverted system and the pressure regulating valve of the converted system;
and when a three-level alarm occurs, opening the nitrogen feeding regulating valve.
6. The multi-level control method for preventing shift reactor runaway as recited in claim 5, wherein: the temperature high alarm is set to a value between 420 and 450 ℃, the oxygen content high alarm is set to a value between 0.1 and 0.24 percent v/v, the temperature high alarm is set to a value between 440 and 470 ℃, the oxygen content high alarm is set to a value between 0.15 and 0.36 percent v/v, the temperature high interlock value is set to a value between 460 and 490 ℃, and the oxygen content high interlock value is set to a value between 0.2 and 0.48 percent v/v.
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