CN114425273A - Control method and application of carbo-hydrogenation reactor - Google Patents
Control method and application of carbo-hydrogenation reactor Download PDFInfo
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- C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
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Abstract
The invention discloses a control method and application of a carbo-hydrogenation reactor. The control method of the carbon hydrogenation reactor comprises the following steps: acquiring the total number of the bed layers of the multi-section bed carbon hydrogenation reactor and the volume content of acetylene in the real-time total inlet material of the multi-section bed carbon hydrogenation reactor; obtaining the acetylene hydrogenation conversion rate set value C of each stage of bed carbon dioxide hydrogenation reactor except the last stage of bednObtaining the acetylene hydrogenation conversion rate set value of the final-stage bed hydrogenation reactor; obtaining the actual value C 'of the acetylene hydrogenation conversion rate of each bed of the carbon dioxide hydrogenation reactor'nAccording to the actual value C 'of the acetylene hydrogenation conversion rate of each bed of the carbon hydrogenation reactor'nAdjusting the operating conditions of each bed of the carbon hydrogenation reactorAnd the difference between the actual value of the acetylene hydrogenation conversion rate and the set value of each bed of the carbon hydrogenation reactor is positioned in the set parameter. The method achieves the purposes of improving the operation stability of the medium carbon dehydrogenation reactor, obtaining the optimal ethylene yield, improving the ethylene yield and prolonging the operation period of the catalyst.
Description
Technical Field
The invention belongs to the field of petrochemical industry, and particularly relates to a control method and application of a carbon dioxide hydrogenation reactor.
Background
Ethylene technology is the leading technology of petrochemical industry, and the ethylene technology level is regarded as an important mark for measuring the development level of the petrochemical industry in China. Trienes (ethylene, propylene, butadiene) produced by an ethylene cracking device are basic raw materials of petrochemical industry, and the high and low yield of the trienes is a main mark for measuring the development level of the national petrochemical industry.
After the liquid hydrocarbon raw materials such as naphtha and the like in the ethylene cracking device are subjected to steam cracking and separation, the carbon-two fraction contains ethylene, ethane and a small amount of acetylene, and the content of the acetylene is about 0.5-3 percent (volume). In downstream polymerization reactions, the presence of acetylene poisons the polyolefin promoters and must be removed to obtain polymer grade ethylene. The acetylene removal method widely used at present is a catalytic selective hydrogenation method. The acetylene in the carbon dioxide fraction is removed by two processes, namely a solvent absorption method and a catalytic selective hydrogenation method.
The catalytic selective hydrogenation method has the advantages of simple process flow, less energy consumption, no environmental pollution, increase of the yield of target products, and increasingly common application of the hydrogenation method along with the continuous improvement of the performance of novel efficient hydrogenation catalysts, thereby becoming the most common economic and simple method at present. Depending on the process route, it can be divided into two types of hydrogenation, namely pre-hydrogenation and post-hydrogenation. The post-hydrogenation process is suitable for separation processes mainly comprising sequential separation, pre-depropanization and post-hydrogenation, pre-deethanization and post-hydrogenation and the like, and is a process of adding a proper amount of hydrogen into the remaining pure carbon two fraction for hydrogenation after light fractions containing hydrogen, CO, methane and the like and heavy fractions containing three or more carbon atoms and the like in the pyrolysis gas.
The carbon hydrogenation reactor unit is an important link for refining ethylene products, and is used for selectively hydrogenating acetylene in the carbon-containing fraction into ethylene under the action of a catalyst. Ethylene loss if excess hydrogenation of acetylene to ethane results; or acetylene is polymerized to generate oligomers or even high polymers, which affects the service cycle of the reactor; if the acetylene hydrogenation activity is not good, the concentration of the acetylene at the outlet of the reactor cannot be controlled within the index requirement range, and the ethylene product is unqualified, which can directly affect the ethylene product and a downstream industrial chain, so that the operation quality of the carbon dioxide hydrogenation reactor plays a vital role in both enterprise benefit and national civilization.
The carbon dioxide hydrogenation catalyst generally adopts palladium noble metal as an active component, and the production suppliers comprise China petrochemical catalyst company, Clariant company, PHILIPS company and the like. The thermodynamic parameters, the surface adsorption and desorption reaction rates and the process sensitivity of each brand of catalyst of each manufacturer are different, and the optimal performance can be ensured by targeted adjustment and optimization.
At present, the production control of the carbon dioxide hydrogenation reactor generally adopts manual regulation and control, and technicians manually regulate and control related parameters. Because the cracking separation process is long, the process is complex, the labor is limited, and the carbon dioxide hydrogenation reactor cannot be monitored, adjusted and optimized in real time. When the carbon dioxide hydrogenation system has unstable conditions such as material composition, pressure, temperature, flow, hydrogen fluctuation and the like, the stability recovery is very slow by the hydrogenation system, and the superposition phenomenon generated by multiple fluctuations makes the system in a metastable state for a long time, so that acetylene leakage and ethylene loss at the outlet of the reactor are easily caused, and the ethylene yield and the separation effect of the rectifying tower are influenced.
At present, the operation of a carbon dioxide hydrogenation reactor adopts a method of manual experience and manual regulation, and is influenced by the performance of a catalyst and the design of the reactor, the difficulty of the cooperative control of each section of bed of a multi-section bed carbon dioxide hydrogenation reactor is large, and the problems of frequent over-hydrogenation or insufficient hydrogenation result in low total ethylene selectivity or acetylene leakage of the multi-section bed carbon dioxide hydrogenation reactor. The overload operation of the individual bed reactor shortens the whole service cycle of the carbon hydrogenation reactor.
Disclosure of Invention
In view of this, the invention provides a control method and application of a carbon two hydrogenation reactor, which at least solve the problems of poor operation stability and low ethylene yield of the carbon two hydrogenation reactor in the prior art.
In a first aspect, the present invention provides a method for controlling a carbon dioxide hydrogenation reactor, comprising:
acquiring the total number of the bed layers of the multi-section bed carbon hydrogenation reactor and the volume content of acetylene in the real-time total inlet material of the multi-section bed carbon hydrogenation reactor;
obtaining the acetylene hydrogenation conversion rate set value C of each stage of bed carbon hydrogenation reactor except the last stage of bed based on the total stage number of the beds and the volume content of acetylene in the real-time total inlet materialnBased on the acetylene hydroconversion setpoint CnObtaining the acetylene hydrogenation conversion rate set value of the final-stage bed carbon dioxide hydrogenation reactor;
obtaining the actual value C 'of the acetylene hydrogenation conversion rate of each bed of the carbon dioxide hydrogenation reactor'n，
According to the actual value C 'of the acetylene hydrogenation conversion rate of each bed of the carbon dioxide hydrogenation reactor'nAnd adjusting the operating conditions of each stage of the carbon dioxide hydrogenation reactor to ensure that the difference between the actual value of the acetylene hydrogenation conversion rate and the set value of each stage of the carbon dioxide hydrogenation reactor is within the set parameters.
Optionally, the acetylene hydrogenation conversion rate set value C of each stage of the carbon dioxide hydrogenation reactor except the last stage of the bed is obtained based on the total stage number of the bed and the volume content of acetylene in the real-time total inlet materialnThe method comprises the following steps:
establishing a multi-section bed acetylene hydrogenation conversion rate calculation model;
the calculation model of the acetylene hydrogenation conversion rate of the multi-section bed obtains the acetylene hydrogenation of each section of bed carbon hydrogenation reactor except the last section bed based on the total section number of the bed and the volume content of the acetylene in the real-time total inlet materialHydrogen conversion setpoint Cn。
Optionally, the calculation model of the multi-stage bed acetylene hydrogenation conversion rate is as follows:
wherein, CnSetting the acetylene hydrogenation conversion rate of the nth-stage bed hydrogenation reactor, wherein X is the volume content of acetylene in the real-time total inlet material of the multistage bed hydrogenation reactor, N is the total number of stages of the bed layer of the multistage bed hydrogenation reactor, and d is a model constant; bn、mn、kn、lnAssigning coefficients to the nth segment, where N is 1, 2, … (N-1), aiThe factor is the influence factor of the number of segments and is influenced by the total number of segments N, wherein i is 1, 2, … (N-1).
Optionally, the difference between the actual value of the acetylene hydrogenation conversion rate and the set value of each bed of the carbon dioxide hydrogenation reactor within the set parameters is as follows:
the absolute value of the difference between the actual value of the acetylene hydrogenation conversion rate and the set value of each bed of the carbon hydrogenation reactor is less than 5 percent.
Optionally, X is the volume content of acetylene in the real-time total inlet material of the multi-stage bed hydrogenation reactor, and the value of X is more than or equal to 0.3% and less than or equal to 5.2%;
n is the total number of the sections of the multi-section bed carbon dioxide hydrogenation reactor, and the value of N is an integer which is more than 1 and less than 6;
said C isnWherein N is 1, 2, … (N-1).
Optionally, the set point C based on the acetylene hydroconversion ratenThe acetylene hydrogenation conversion rate set value of the final-stage bed hydrogenation reactor is obtained by the following steps:
optionally, obtaining an actual acetylene hydrogenation conversion rate C 'of each bed of carbon dioxide hydrogenation reactor'nComprises the following steps:
of formula (II) to C'nThe actual value of the acetylene hydrogenation conversion rate is obtained; xn inletThe volume content of acetylene in the inlet material of the nth section bed; xn outletThe volume content of acetylene in the outlet material of the nth section bed is shown, wherein N is 1, 2, … (N-1).
Optionally, the operating parameters of the operating conditions include the inlet material temperature and the hydrogen acetylene ratio of the carbon dioxide hydrogenation reactor of each stage of bed except the last stage of bed;
the adjusting of the operating conditions of each stage of the carbon dioxide hydrogenation reactor to enable the difference between the actual value of the acetylene hydrogenation conversion rate and the set value of each stage of the carbon dioxide hydrogenation reactor to be within the set parameters comprises the following steps:
when the absolute value of the difference between the actual value of the acetylene hydrogenation conversion rate of the hydrogenation reactor for the second section of bed and the set value is within the set parameter, the operation parameter of the second section of bed is not adjusted;
when the difference value between the actual value of the acetylene hydrogenation conversion rate of the hydrogenation reactor of the nth section of bed and the set value is more than or equal to the maximum value of the set parameter, reducing the operating parameter of the nth section of bed;
when the difference value between the actual value of the acetylene hydrogenation conversion rate of the hydrogenation reactor for the second section of bed and the set value is less than or equal to the minimum value of the set parameter, improving the operation parameters of the second section of bed;
wherein N is 1, 2, … (N-1).
Optionally, the reducing the nth section bed operating parameter comprises: preferentially reducing the hydrogen alkyne ratio;
the increasing the nth section bed operating parameters comprises: the hydrogen alkyne ratio is preferentially increased.
Optionally, the adjustment range of the inlet material temperature of the carbon dioxide hydrogenation reactor of each stage of bed except the last stage of bed is 30-65 ℃, and preferably 35-56 ℃.
Optionally, the adjusting rate of the inlet material temperature of the carbon dioxide hydrogenation reactor of each stage of bed except the last stage of bed is in the range of 0.5-10 ℃/hour, preferably 2.0-6.0 ℃/hour.
Optionally, the adjustment range of the hydrogen alkyne ratio of each stage of the carbon dioxide hydrogenation reactor except the final stage of the bed is 0.5-4.0, and preferably 0.8-3.6.
Optionally, the adjusting rate of the hydrogen alkyne ratio of each stage of the carbon dioxide hydrogenation reactor except the final stage of the bed is in the range of 0.01-0.4/hour, and preferably 0.04-0.2/hour.
Optionally, the inlet material of the multi-stage bed carbon dioxide hydrogenation reactor at least comprises ethylene, ethane and acetylene;
the inlet material of the multi-section bed carbon dioxide hydrogenation reactor also comprises at least one of hydrogen, methane, propylene and propane.
Optionally, the volume content of acetylene in the inlet material of the multi-stage bed hydrogenation reactor is at least more than 0.25% and less than 5.6%.
In a second aspect, the invention provides a method for refining ethylene and removing acetylene by hydrogenation, which is applied to a separation process of an ethylene cracking device, wherein the separation process comprises a sequential separation process, a front-end depropanization and rear-end hydrogenation process and a front-end deethanization and rear-end hydrogenation process, and any one of the control methods of the first aspect is used. .
The operation conditions of each segment of the carbon dioxide hydrogenation reactor are adjusted based on the acetylene hydrogenation conversion rate set value of each segment of the carbon dioxide hydrogenation reactor and the acetylene hydrogenation conversion rate actual value of each segment of the carbon dioxide hydrogenation reactor, so that the difference between the acetylene hydrogenation conversion rate actual value and the set value of each segment of the carbon dioxide hydrogenation reactor is positioned in the set parameters. Therefore, the difficulty of cooperative control of each section of bed is reduced, the problem of frequent over-hydrogenation or insufficient hydrogenation is avoided, and the purposes of improving the operation stability of the medium carbon-two hydrogenation reactor, obtaining the optimal ethylene yield, improving the ethylene yield and prolonging the operation period of the catalyst are achieved.
Drawings
Exemplary embodiments of the present invention will be described in more detail by referring to the accompanying drawings.
FIG. 1 shows a flow diagram of a method of controlling a carbo-hydrogenation reactor according to one embodiment of the invention;
FIG. 2 shows a block diagram of a multi-stage bed carbon two hydrogenation reactor according to one embodiment of the present invention;
FIG. 3 illustrates a functional block diagram of a multi-stage bed carbon two hydrogenation reactor control system according to one embodiment of the present invention;
wherein:
1-the 1 st stage bed hydrogenation reactor, 2-the 2 nd stage bed hydrogenation reactor, 3-the 3 rd stage bed hydrogenation reactor, 4-the last stage bed hydrogenation reactor, 5-the ethylene rectifying tower, 6-the condenser.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The present invention will be further described with reference to the following examples, but the scope of the present invention is not limited to these examples.
The multi-stage bed and the final stage bed are the carbon dioxide hydrogenation reactors of the corresponding stage beds. The multi-section bed carbon dioxide hydrogenation reactor is a multi-section bed series connection carbon dioxide hydrogenation reactor system; each reactor section of the multi-section bed carbon dioxide hydrogenation reactor is designed into an adiabatic bed or an isothermal bed.
The principal operating conditions for a carbon dioxide hydrogenation reactor are two: the hydrogen to acetylene ratio and the inlet feed temperature.
The first embodiment is as follows:
as shown in fig. 1, a method for controlling a carbon hydrogenation reactor includes:
step S101: acquiring the total number of the bed layers of the multi-section bed carbon hydrogenation reactor and the volume content of acetylene in the real-time total inlet material of the multi-section bed carbon hydrogenation reactor;
the volume content of acetylene in the real-time total inlet material of the multi-section bed carbon dioxide hydrogenation reactor is obtained based on the input parameters of a controller of the multi-section bed carbon dioxide hydrogenation reactor, and the input parameters of the controller include but are not limited to the inlet material temperature of each section bed (not including the last section bed) of the multi-section bed carbon dioxide hydrogenation reactor, the inlet material pressure of the multi-section bed carbon dioxide hydrogenation reactor, the inlet material flow of the multi-section bed carbon dioxide hydrogenation reactor, the inlet acetylene concentration of each section bed (not including the last section bed) of the multi-section bed carbon dioxide hydrogenation reactor, the inlet hydrogen flow and concentration of each section bed (not including the last section bed) of the multi-section bed carbon dioxide hydrogenation reactor, the outlet acetylene concentration of each section bed (not including the last section bed) of the multi-section bed carbon dioxide hydrogenation reactor and the like.
Step S102: obtaining the acetylene hydrogenation conversion rate set value C of each stage of bed carbon hydrogenation reactor except the last stage of bed based on the total stage number of the beds and the volume content of acetylene in the real-time total inlet materialnBased on the acetylene hydroconversion setpoint CnObtaining the acetylene hydrogenation conversion rate set value of the final-stage bed carbon dioxide hydrogenation reactor;
step S103: obtaining the actual value C 'of the acetylene hydrogenation conversion rate of each bed of the carbon dioxide hydrogenation reactor'n，
Step S104: according to the actual value C 'of the acetylene hydrogenation conversion rate of each bed of the carbon dioxide hydrogenation reactor'nAnd adjusting the operating conditions of each stage of the carbon dioxide hydrogenation reactor to ensure that the difference between the actual value of the acetylene hydrogenation conversion rate and the set value of each stage of the carbon dioxide hydrogenation reactor is within the set parameters.
Optionally, the acetylene hydrogenation conversion rate set value C of each stage of the carbon dioxide hydrogenation reactor except the last stage of the bed is obtained based on the total stage number of the bed and the volume content of acetylene in the real-time total inlet materialnThe method comprises the following steps:
establishing a multi-section bed acetylene hydrogenation conversion rate calculation model;
the calculation model of the acetylene hydrogenation conversion rate of the multi-section bed obtains the acetylene hydrogenation conversion rate set value C of each section of bed carbon hydrogenation reactor except the last section bed based on the total section number of the bed layers and the volume content of acetylene in the real-time total inlet materialn。
Optionally, the calculation model of the multi-stage bed acetylene hydrogenation conversion rate is as follows:
wherein, CnSetting the acetylene hydrogenation conversion rate of the n-th bed hydrogenation reactorSetting a value, wherein X is the volume content of acetylene in the real-time total inlet material of the multi-section bed carbon dioxide hydrogenation reactor, N is the total number of sections of the bed layer of the multi-section bed carbon dioxide hydrogenation reactor, and d is a model constant; bn、mn、kn、lnAssigning coefficients to the nth segment, where N is 1, 2, … (N-1), aiThe factor is the influence factor of the number of segments and is influenced by the total number of segments N, wherein i is 1, 2, … (N-1).
Optionally, the difference between the actual value of the acetylene hydrogenation conversion rate and the set value of each bed of the carbon dioxide hydrogenation reactor within the set parameters is as follows:
the absolute value of the difference between the actual value of the acetylene hydrogenation conversion rate and the set value of each bed of the carbon hydrogenation reactor is less than 5 percent.
Absolute value | C 'of difference between actual value of acetylene hydrogenation conversion rate and set value of each bed'n-Cn|＜5％。
Optionally, X is the volume content of acetylene in the real-time total inlet material of the multi-stage bed hydrogenation reactor, and the value of X is more than or equal to 0.3% and less than or equal to 5.2%;
n is the total number of the sections of the multi-section bed carbon dioxide hydrogenation reactor, and the value of N is an integer which is more than 1 and less than 6;
said C isnWherein N is 1, 2, … (N-1).
Optionally, the set point C based on the acetylene hydroconversion ratenThe acetylene hydrogenation conversion rate set value of the final-stage bed hydrogenation reactor is obtained by the following steps:
optionally, obtaining an actual acetylene hydrogenation conversion rate C 'of each bed of carbon dioxide hydrogenation reactor'nComprises the following steps:
of formula (II) to C'nThe actual value of the acetylene hydrogenation conversion rate is obtained; xn inletIs the nth segmentAcetylene volume content in the bed inlet feed; xn outletThe volume content of acetylene in the outlet material of the nth section bed is shown, wherein N is 1, 2, … (N-1).
Optionally, the operating parameters of the operating conditions include the inlet material temperature and the hydrogen acetylene ratio of the carbon dioxide hydrogenation reactor of each stage of bed except the last stage of bed;
the adjusting of the operating conditions of each stage of the carbon dioxide hydrogenation reactor to enable the difference between the actual value of the acetylene hydrogenation conversion rate and the set value of each stage of the carbon dioxide hydrogenation reactor to be within the set parameters comprises the following steps:
when the absolute value of the difference between the actual value of the acetylene hydrogenation conversion rate of the hydrogenation reactor for the second section of bed and the set value is within the set parameter, the operation parameter of the second section of bed is not adjusted;
when the difference value between the actual value of the acetylene hydrogenation conversion rate of the hydrogenation reactor of the nth section of bed and the set value is more than or equal to the maximum value of the set parameter, reducing the operating parameter of the nth section of bed;
when the difference value between the actual value of the acetylene hydrogenation conversion rate of the hydrogenation reactor for the second section of bed and the set value is less than or equal to the minimum value of the set parameter, improving the operation parameters of the second section of bed;
wherein N is 1, 2, … (N-1).
(a) Absolute value | C 'of difference between actual value of acetylene hydrogenation conversion rate of nth-stage bed and set value'n-CnWhen the absolute value is less than 5 percent, the operation parameters of the nth section bed are not adjusted;
(b) the difference between the actual value of the acetylene hydrogenation conversion rate of the nth stage bed and the set value (C'n-Cn) When the concentration is more than or equal to 5 percent, reducing the temperature of the material at the inlet of the nth stage bed and the hydrogen-acetylene ratio, and preferentially reducing the hydrogen-acetylene ratio until the absolute value of the difference between the actual value of the acetylene hydrogenation conversion rate of the nth stage bed and the set value is | C'n-CnLess than 5%;
(c) the difference between the actual value of the acetylene hydrogenation conversion rate of the nth stage bed and the set value (C'n-Cn) When the concentration is less than or equal to-5%, the temperature of the material at the inlet of the nth stage bed and the hydrogen acetylene ratio are increased, the hydrogen acetylene ratio is preferentially increased until the absolute value of the difference between the actual value of the acetylene hydrogenation conversion rate of the nth stage bed and the set value is | C'n-CnLess than 5%.
Optionally, the reducing the nth section bed operating parameter comprises: preferentially reducing the hydrogen alkyne ratio;
the increasing the nth section bed operating parameters comprises: the hydrogen alkyne ratio is preferentially increased.
Optionally, the adjustment range of the inlet material temperature of the carbon dioxide hydrogenation reactor of each stage of bed except the last stage of bed is 30-65 ℃, and preferably 35-56 ℃.
The inlet material temperature can be 30 deg.C, 33 deg.C, 35 deg.C, 40 deg.C, 45 deg.C, 50 deg.C, 56 deg.C, 60 deg.C or 65 deg.C.
Optionally, the adjusting rate of the inlet material temperature of the carbon dioxide hydrogenation reactor of each stage of bed except the last stage of bed is in the range of 0.5-10 ℃/hour, preferably 2.0-6.0 ℃/hour.
The specific rate of adjustment of the inlet material temperature may be 0.5 ℃/hr, 1.0 ℃/hr, 1.5 ℃/hr, 2.0 ℃/hr, 2.5 ℃/hr, 3.0 ℃/hr, 3.5 ℃/hr, 4.0 ℃/hr, 5.0 ℃/hr, 6.0 ℃/hr, 7.0 ℃/hr, 8.0 ℃/hr, 9.0 ℃/hr, or 10 ℃/hr.
Optionally, the adjustment range of the hydrogen alkyne ratio of each stage of the carbon dioxide hydrogenation reactor except the final stage of the bed is 0.5-4.0, and preferably 0.8-3.6.
The specific adjustment range of the hydrogen alkyne ratio can be as follows: 0.5, 0.6, 0.7, 0.8, 1.0, 2.0, 3.0, 3.6 or 4.0.
Optionally, the adjusting rate of the hydrogen alkyne ratio of each stage of the carbon dioxide hydrogenation reactor except the final stage of the bed is in the range of 0.01-0.4/hour, and preferably 0.04-0.2/hour.
The rate of adjustment of the specific hydroacetylene ratio may be 0.01/hr, 0.04/hr, 0.10/hr, 0.15/hr, 0.20/hr, 0.25/hr, 0.30/hr, 0.35/hr, or 0.40/hr.
Optionally, the inlet material of the multi-stage bed carbon dioxide hydrogenation reactor at least comprises ethylene, ethane and acetylene;
the inlet material of the multi-section bed carbon dioxide hydrogenation reactor also comprises at least one of hydrogen, methane, propylene and propane.
Optionally, the volume content of acetylene in the inlet material of the multi-stage bed hydrogenation reactor is at least more than 0.25% and less than 5.6%.
In this embodiment, during the production process of the carbon dioxide hydrogenation reactor, a calculation model of the acetylene hydrogenation conversion rate of the multi-stage bed is built, and the set value C of the acetylene hydrogenation conversion rate of each stage is calculated in real timenThe controller is used for controlling the acetylene hydrogenation conversion rate of each section of bed to be actually C'nAdjusting the operation conditions of each stage of the bed reactor to keep the absolute value of the difference between the actual value of the acetylene hydrogenation conversion rate and the set value of each stage of the bed at | C'n-CnIn the range of | < 5%.
More specifically, based on the optimization of the carbon dioxide hydrogenation reaction characteristics and the related catalyst control parameters, a calculation model of acetylene hydrogenation conversion rate of a multi-section bed is established, and the acetylene hydrogenation conversion rate set value C of each section of bed is solved and given according to the total number of sections of the bed of the carbon dioxide hydrogenation reactor and the volume content of acetylene in the material at the total inlet of the real-time reactornThe expression is as follows:
in the formula, CnThe value is the set value of the acetylene hydrogenation conversion rate of the nth section bed; x is the volume content of acetylene in the total inlet material of the carbon hydrogenation reactor; n is the total number of the sections of the multi-section bed hydrogenation reactor; d is a model constant; bn、mn、kn、lnAssigning a coefficient to the nth segment, wherein N is 1, 2, … (N-1); a isiThe factor is the influence factor of the number of segments and is influenced by the total number of segments N, wherein i is 1, 2, … (N-1).
N in the calculation model of the multi-section bed acetylene hydrogenation conversion rate is the total number of sections of the multi-section bed carbon dioxide hydrogenation reactor, and the value range is as follows: n is more than 1 and less than 6; x is the volume content of acetylene at the total inlet of the reactor, and the value range of X is more than or equal to 0.3% and less than or equal to 5.2%; cnAnd (3) calculating the set value of the acetylene hydrogenation conversion rate of the nth section bed obtained by model calculation according to a multistage bed acetylene hydrogenation load distribution model, wherein N is 1, 2, … (N-1).
The calculation model of acetylene hydrogenation conversion rate of the multi-section bed is suitable for the two-section bed and the above carbon hydrogenation reactors; the calculation model of the acetylene hydrogenation conversion rate of the multi-section bed is not used for calculating the set value of the acetylene hydrogenation conversion rate of the last section bed of the multi-section bed carbon dioxide hydrogenation reactor. The method for calculating the acetylene conversion rate of the final bed of the multi-stage bed carbon dioxide hydrogenation reactor comprises the following steps:
the method for calculating the actual value of the acetylene hydrogenation conversion rate of each bed in the multi-stage bed carbon dioxide hydrogenation reactor comprises the following steps:
of formula (II) to C'nThe actual value of the acetylene hydrogenation conversion rate is obtained; xn inletThe volume content of acetylene in the inlet material of the nth section bed; xn outletThe volume content of acetylene in the outlet material of the nth section bed is shown, wherein N is 1, 2, … (N-1).
The input parameters of the controller include, but are not limited to, the inlet material temperature of each section of bed (excluding the last section of bed) of the multi-section bed carbon dioxide hydrogenation reactor, the inlet material pressure of the multi-section bed carbon dioxide hydrogenation reactor, the inlet material flow rate of the multi-section bed carbon dioxide hydrogenation reactor, the inlet acetylene concentration of each section of bed (excluding the last section of bed) of the multi-section bed carbon dioxide hydrogenation reactor, the inlet hydrogen flow and concentration of each section of bed (excluding the last section of bed) of the multi-section bed carbon dioxide hydrogenation reactor, the outlet acetylene concentration of each section of bed (excluding the last section of bed) of the multi-section bed carbon dioxide hydrogenation reactor, and the like.
The controller adjusts the operation parameters of the carbon dioxide hydrogenation reactor to the reactor inlet material temperature and the hydrogen acetylene ratio of each section of bed (excluding the tail section of bed):
(a) the absolute value | C 'of the difference between the actual value of the acetylene hydrogenation conversion rate of the nth stage bed and the set value'n-CnWhen the absolute value is less than 5 percent, the operation parameters of the nth section bed are not adjusted;
(b) the actual hydrogenation conversion rate of the acetylene in the nth section bedValue and set value difference (C'n-Cn) When the concentration is more than or equal to 5 percent, reducing the temperature of the material at the inlet of the nth stage bed and the hydrogen-acetylene ratio, and preferentially reducing the hydrogen-acetylene ratio until the absolute value of the difference between the actual value of the acetylene hydrogenation conversion rate of the nth stage bed and the set value is | C'n-CnLess than 5%;
(c) the actual value of the acetylene hydrogenation conversion rate of the nth stage bed is different from the set value (C'n-Cn) When the concentration is less than or equal to-5%, the temperature of the material at the inlet of the nth stage bed and the hydrogen acetylene ratio are increased, the hydrogen acetylene ratio is preferentially increased until the absolute value of the difference between the actual value of the acetylene hydrogenation conversion rate of the nth stage bed and the set value is | C'n-CnLess than 5%.
The multi-section bed carbon dioxide hydrogenation reactor is a multi-section bed series connection carbon dioxide hydrogenation reactor system; each section of bed reactor of the multi-section bed carbon hydrogenation reactor is designed into a heat insulation bed or an isothermal bed; the number of reactors in the multi-stage bed carbon dioxide hydrogenation reactor is more than 1 and less than 6.
The inlet material temperature of each stage bed (excluding the final stage bed) of the carbon hydrogenation reaction chamber is adjusted within the range of 30-65 ℃, preferably 385-56 ℃.
The adjusting rate of the inlet material temperature of each stage bed (excluding the final stage bed) of the carbon dioxide hydrogenation reactor is in the range of 0.5-10 ℃/hour, preferably 2.0-6.0 ℃/hour.
The adjustment range of the hydrogen acetylene ratio of each stage bed (excluding the final stage bed) of the carbon hydrogenation reaction chamber is 0.5-4.0, preferably 0.8-3.6.
The adjustment rate of the hydrogen acetylene ratio of each stage bed (excluding the last stage bed) of the carbon dioxide hydrogenation reactor is in the range of 0.01 to 0.4/hour, preferably 0.04 to 0.2/hour.
In the present embodiment, the concentration refers to the volume percentage content, and the flow refers to the mass flow.
In the automatic control process of the carbon hydrogenation reactor, the difference between the actual value of the acetylene hydrogenation conversion rate of the nth stage bed and the set value is controlled to be-5% < (C'n-Cn) In the range of < 5%. If the difference between the actual value of the acetylene hydrogenation conversion rate of the nth bed and the set value is too low or too high, the acetylene hydrogenation load distribution is not uniform, which is not favorable for the overall optimization operation of the multi-section bed carbon dioxide hydrogenation reactorAnd as a result, the total selectivity of ethylene is reduced.
In the control logic program of the carbon dioxide hydrogenation reactor, the regulation principle is that the actual value of the acetylene hydrogenation conversion rate of the nth stage bed is different from the set value (C'n-Cn) When the concentration of the hydrogen and alkyne in the feed is more than or equal to 5 percent, reducing the temperature of the feed at the inlet of the nth section of the bed and the hydrogen and alkyne ratio, preferentially reducing the hydrogen and alkyne ratio, and then adjusting the temperature of the feed at the inlet; the difference between the actual value of the acetylene hydrogenation conversion rate of the nth stage bed and the set value (C'n-Cn) And when the temperature is less than or equal to-5%, the material temperature and the hydrogen alkyne ratio of the inlet of the nth section of bed are increased, the hydrogen alkyne ratio is preferentially increased, and the material temperature of the inlet is adjusted. And a control logic program of the carbon hydrogenation reactor calculates according to the actual value and the set value of the acetylene hydrogenation conversion rate, and automatically adjusts the material temperature and the hydrogen acetylene ratio of each section of the bed mouth of the carbon hydrogenation reactor. When the difference value between the actual value of the acetylene hydrogenation conversion rate of the nth section of bed and the set value exceeds the upper limit and the lower limit, two operation parameters can be simultaneously adjusted, and the adjusting rate is the lower limit of the adjustable range.
In the process of adjusting various control variables of hydrogenation by a control logic program of the carbo-hydrogenation reactor, the adjustment range of the hydrogen alkyne ratio of each section of bed of the carbo-hydrogenation reactor is 0.5-4.0, preferably 0.8-3.6; the adjusting range of the inlet material temperature of each section of bed of the carbon hydrogenation reactor is 30-65 ℃, and the preferable range is 35-56 ℃. If an operating parameter reaches an upper limit, the parameter is kept unchanged to adjust another operating variable. If the inlet material temperature and the hydrogen acetylene ratio both reach the upper limit and cannot meet the requirements, the operation mode is automatically switched into a manual mode and an alarm is given.
The standard of the automatic control system of the carbon dioxide hydrogenation reactor is whether the absolute value of the difference between the actual value of the acetylene hydrogenation conversion rate of each section of bed and the set value accords with | C'n-CnRange criteria of | < 5% were performed.
In the automatic control process of the carbon dioxide hydrogenation reactor, the adjustment rate range of the inlet material temperature of each section of bed (excluding the last section of bed) of the multi-section bed carbon dioxide hydrogenation reactor is generally 0.5-10 ℃/hour, and preferably 2.0-6.0 ℃/hour; the adjustment rate of the hydrogen acetylene ratio of each stage bed (excluding the final stage bed) of the multi-stage bed hydrogenation reactor is in the range of 0.01-0.4/hr, preferably 0.04-0.2/hr. When saidIs the difference (C ') between the actual value of the acetylene hydrogenation conversion rate of the nth bed and the set value'n-Cn) Below-10% or above 10%, simultaneous adjustment of both operating parameters may be used, the rate of adjustment typically being at the lower end of the adjustable rate range. If the difference between the actual value of the acetylene hydrogenation conversion rate of the nth stage bed and the set value is-5% < (C'n-Cn) In the range of < 5%, no adjustments are usually made to the operation to maintain the smoothness of the production operation.
The automatic control method of the carbon hydrogenation reactor is not used for the automatic control of the single-stage bed carbon hydrogenation reactor and the final stage bed in the multi-stage bed carbon hydrogenation reactor.
The automatic control method of the carbon dioxide hydrogenation reactor does not need to be matched with hydrogenation moderators such as crude hydrogen, CO and the like.
The automatic control method of the carbon dioxide hydrogenation reactor is applied to a process for refining ethylene and removing acetylene by hydrogenation in a separation process of an ethylene cracking device, wherein the separation process comprises a sequential separation process, a front-end depropanization and rear-end hydrogenation process, a front-end deethanization and rear-end hydrogenation process and the like.
The composition of the inlet material of the multi-stage bed carbon dioxide hydrogenation reactor at least contains ethylene, ethane and acetylene, and also comprises at least one of hydrogen, methane, propylene and propane. The volume content of acetylene in the total inlet material composition of the multi-section bed hydrogenation reactor is at least more than 0.25 percent and less than 5.6 percent.
The automatic control of the carbon dioxide hydrogenation reactor comprises two steps: a program initialization phase and an automatic control phase. The execution sequence of the automatic control program is as follows:
1. modeling
And establishing a multi-section bed acetylene hydrogenation conversion rate calculation model, and assigning values to model constants, distribution coefficients of each section and influence factors of the number of the sections in the model according to the catalyst operating characteristics, the composition of the carbon dioxide material and reactor design parameters. Solving to give a set value C of acetylene hydrogenation conversion rate of each section of bedn。
2. Program initialization phase
After the program is started, initializing internal variables such as the hydrogen acetylene ratio, the inlet material temperature and the like of the multi-section bed carbon dioxide hydrogenation reactor, and automatically identifying data signals of acetylene concentration at the inlet and the outlet of each section of bed.
And confirming that all field operations are executed by an operator, inputting normal field analysis data, and preparing to enter an automatic control stage, wherein if the field analysis data are not confirmed, the program is in a waiting state until all the field analysis data are confirmed. And (4) clicking by an operator to assign and confirm the total segment number N of the carbon hydrogenation reactor, and entering an automatic control stage.
3. Self-control phase
After entering the automatic control program, the control logic program obtains the field process and analysis data according to the DCS system of the carbon dioxide hydrogenation reactor, and judges whether each control variable in each section of bed reactor needs to be adjusted every 1-1800 seconds according to the model calculation and judgment principle, thereby realizing the automatic control of each parameter in the production process of the carbon dioxide hydrogenation reactor. The shorter the time interval for adjusting the parameters, the better, but at the same time, the feedback time for adjusting the control variable signal and the time interval for analyzing the data are taken into account.
In the automatic production control process of the carbon dioxide hydrogenation reactor, an automatic control program monitors important variables such as inlet material temperature, hydrogen alkyne ratio, catalyst bed layer temperature and the like, and once the deviation is overlarge, the program enters a holding state, and simultaneously displays alarm information and gives an audible alarm.
Example two:
a method for removing acetylene by ethylene refining and hydrogenation is applied to a separation process of an ethylene cracking device, wherein the separation process comprises a sequential separation process, a hydrogenation process after front depropanization and a hydrogenation process after front deethanization, and the control method in the embodiment is used.
As shown in fig. 2, the multi-stage bed carbo-hydrogenation reactor is a multi-stage bed series carbo-hydrogenation reactor system; each reactor section of the multi-section bed carbon dioxide hydrogenation reactor is designed into an adiabatic bed or an isothermal bed. In fig. 2, four-stage bed reactors are included, namely a first-stage bed reactor, a second-stage bed reactor, a third-stage bed reactor and a last-stage bed reactor. The inlet material raw material and hydrogen gas are reacted in the first-stage bed reactor, then enter the second-stage bed reactor through a condenser, are treated in the second-stage bed reactor, then react with the entered hydrogen gas in the third-stage bed reactor, then enter the last-stage bed reactor through the condenser, and the product of the last-stage bed reactor enters the ethylene rectifying tower through the condenser.
The method of the invention is applied to a carbon hydrogenation reactor of the olefin plant: and adding a controller connected with an OPC server of the original system outside the original DCS, as shown in fig. 3, adjusting the process conditions of the 1 st-stage bed and the 2 nd-stage carbohydrogenation reactor, and providing the adjustment target to the original DCS in real time so as to realize automatic control of the multi-stage bed carbohydrogenation reactor.
Firstly, assigning values to a multi-stage bed acetylene hydrogenation conversion rate calculation model of a new controller, wherein the distribution coefficients of the 1 st stage, the 2 nd stage and the 3 rd stage are b respectively1＝2.5、m1＝2.5、k1＝21、l1＝120，b2＝0.9、m2＝1.6、k2＝11.7、l2＝100，b3＝3.9、m3＝1.3、k3＝15、l190; number of segments influencing factor a1＝0.371、a2＝0.782、a3From this, the set point C for the hydroconversion of acetylene for each stage is calculated at a total inlet acetylene concentration of 2.5 mol%1＝41.7％、C2＝27.1％、C3＝20.0％、Cend11.2 percent; when the total inlet acetylene concentration is 2.9 mol%, the hydrogenation conversion rate set value C of each section of acetylene1＝38.0％、C2＝28.3％、C3＝21.2％、Cend12.5%. The controller can calculate the C of each section according to the total inlet acetylene concentration and the inlet and outlet acetylene concentrations of each section which are changed in real timenAnd C'nAnd the online control unit automatically controls the inlet material temperature and the hydrogen acetylene ratio of each section of the bed reactor to be adjusted in real time after the judgment of the control system. The automatic control of the end bed judges according to the concentration of the acetylene at the outlet, and the inlet material temperature and the hydrogen acetylene ratio of the end bed are automatically adjusted. The catalyst selectivity of the carbohydrogenator can be increased to 67%.
Comparative example:
an olefin plant producing 150 million tons of ethylene in a year has 12 cracking furnaces, and can process various cracking raw materials from ethane to hydrogenated tail oil and the like. The separation process of the plant adopts a sequential separation flow, a carbon hydrogenation reactor is positioned between a cold zone deethanizer and an ethylene rectifying tower, a four-section bed carbon hydrogenation reactor is designed in series, two four-section bed reactors are opened and standby, and one four-section bed reactor is operated to be a 1 st-section bed reactor, a 2 nd-section bed reactor, a 3 rd-section bed reactor and a last-section bed reactor respectively, as shown in figure 1. When the catalytic activity of the operating four-stage bed reactor cannot meet the production requirements, a standby reactor can be switched in. The catalyst is BC-H-20B developed by the Beijing chemical research institute of the Chinese petrochemical industry.
When the carbon dioxide hydrogenation reactor of the plant operates, the DCS is connected with the online chromatogram, and the online chromatogram analysis data is directly input into the DCS. The flow rate of cold and hot materials in front of the carbon dioxide reactor is controlled by the DCS system, the temperature of the materials at the inlet of each carbon dioxide hydrogenation reactor is kept stable, and the DCS can control the concentration of hydrogen at the inlet of each section to change along with the fluctuation of the concentration of alkyne in the materials so as to keep the hydrogen alkyne ratio constant. The concentration of acetylene in the material is analyzed by an online chromatograph at each section of inlet and outlet of the carbon hydrogenation reactor, the concentration of ethylene in the total inlet material of the four-section bed carbon hydrogenation reactor is 2.3-2.6 mol%, the concentration of acetylene at the outlet is less than 1ppm, and the total selectivity of acetylene and ethylene is maintained at 51%.
The comparison results show that: compared with the manual control of the original factory, the method and the system can obviously improve the selectivity of the carbon dioxide hydrogenation reactor.
Having described embodiments of the present invention, the foregoing description is intended to be exemplary, not exhaustive, and not limited to the embodiments disclosed. Many modifications and variations will be apparent to those of ordinary skill in the art without departing from the scope and spirit of the described embodiments.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
Claims (15)
1. A method of controlling a carbohydrogenator, comprising:
acquiring the total number of the bed layers of the multi-section bed carbon hydrogenation reactor and the volume content of acetylene in the real-time total inlet material of the multi-section bed carbon hydrogenation reactor;
obtaining the acetylene hydrogenation conversion rate set value C of each stage of bed carbon hydrogenation reactor except the last stage of bed based on the total stage number of the beds and the volume content of acetylene in the real-time total inlet materialnBased on the acetylene hydroconversion setpoint CnObtaining the acetylene hydrogenation conversion rate set value of the final-stage bed carbon dioxide hydrogenation reactor;
obtaining the actual value C 'of the acetylene hydrogenation conversion rate of each bed of the carbon dioxide hydrogenation reactor'n，
According to the actual value C 'of the acetylene hydrogenation conversion rate of each bed of the carbon dioxide hydrogenation reactor'nAnd adjusting the operating conditions of each stage of the carbon dioxide hydrogenation reactor to ensure that the difference between the actual value of the acetylene hydrogenation conversion rate and the set value of each stage of the carbon dioxide hydrogenation reactor is within the set parameters.
2. The method for controlling a carbon dioxide hydrogenation reactor as claimed in claim 1, wherein the acetylene hydrogenation conversion rate set value C of each bed carbon dioxide hydrogenation reactor except for the last bed is obtained based on the total number of the bed sections and the volume content of acetylene in the real-time total inlet materialnThe method comprises the following steps:
establishing a multi-section bed acetylene hydrogenation conversion rate calculation model;
the calculation model of the acetylene hydrogenation conversion rate of the multi-section bed obtains the acetylene hydrogenation conversion rate set value C of each section of bed carbon hydrogenation reactor except the last section bed based on the total section number of the bed layers and the volume content of acetylene in the real-time total inlet materialn。
3. The method for controlling a carbon dioxide hydrogenation reactor as claimed in claim 2, wherein the calculation model of the multi-stage bed acetylene hydrogenation conversion rate is:
wherein, CnSetting the acetylene hydrogenation conversion rate of the nth-stage bed hydrogenation reactor, wherein X is the volume content of acetylene in the real-time total inlet material of the multistage bed hydrogenation reactor, N is the total number of stages of the bed layer of the multistage bed hydrogenation reactor, and d is a model constant; bn、mn、kn、lnAssigning coefficients to the nth segment, where N is 1, 2, … (N-1), aiThe factor is the influence factor of the number of segments and is influenced by the total number of segments N, wherein i is 1, 2, … (N-1).
4. The method for controlling the carbon dioxide hydrogenation reactor according to claim 1, wherein the step of enabling the difference between the actual value of the acetylene hydrogenation conversion rate and the set value of each bed of the carbon dioxide hydrogenation reactor to be within the set parameters is as follows:
the absolute value of the difference between the actual value of the acetylene hydrogenation conversion rate and the set value of each bed of the carbon hydrogenation reactor is less than 5 percent.
5. The method for controlling a carbo-hydrogenation reactor as recited in claim 1,
x is the volume content of acetylene in the real-time total inlet material of the multi-stage bed hydrogenation reactor, and the value of X is more than or equal to 0.3% and less than or equal to 5.2%;
n is the total number of the sections of the multi-section bed carbon dioxide hydrogenation reactor, and the value of N is an integer of 1< N < 6;
said C isnWherein N is 1, 2, … (N-1).
6. The method for controlling a carbo-hydrogenation reactor according to claim 1Characterized in that said set point C is based on the acetylene hydroconversion ratenThe acetylene hydrogenation conversion rate set value of the final-stage bed hydrogenation reactor is obtained by the following steps:
7. the method for controlling a carbon dioxide hydrogenation reactor according to claim 1, wherein the actual value C 'of the acetylene hydrogenation conversion rate of each bed of the carbon dioxide hydrogenation reactor is obtained'nComprises the following steps:
of formula (II) to C'nThe actual value of the acetylene hydrogenation conversion rate is obtained; xn inletThe volume content of acetylene in the inlet material of the nth section bed; xn outletThe volume content of acetylene in the outlet material of the nth section bed is shown, wherein N is 1, 2, … (N-1).
8. The method for controlling a carbo-hydrogenation reactor as recited in claim 1, wherein the operation parameters of the operation conditions comprise an inlet material temperature and a hydrogen acetylene ratio of each stage of the carbo-hydrogenation reactor except for the last stage;
the adjusting of the operating conditions of each stage of the carbon dioxide hydrogenation reactor to enable the difference between the actual value of the acetylene hydrogenation conversion rate and the set value of each stage of the carbon dioxide hydrogenation reactor to be within the set parameters comprises the following steps:
when the absolute value of the difference between the actual value of the acetylene hydrogenation conversion rate of the hydrogenation reactor for the second section of bed and the set value is within the set parameter, the operation parameter of the second section of bed is not adjusted;
when the difference value between the actual value of the acetylene hydrogenation conversion rate of the hydrogenation reactor of the nth section of bed and the set value is more than or equal to the maximum value of the set parameter, reducing the operating parameter of the nth section of bed;
when the difference value between the actual value of the acetylene hydrogenation conversion rate of the hydrogenation reactor for the second section of bed and the set value is less than or equal to the minimum value of the set parameter, improving the operation parameters of the second section of bed;
wherein N is 1, 2, … (N-1).
9. The method for controlling a carbo-hydrogenation reactor as recited in claim 8,
the reducing the nth section bed operating parameter comprises: preferentially reducing the hydrogen alkyne ratio;
the increasing the nth section bed operating parameters comprises: the hydrogen alkyne ratio is preferentially increased.
10. A method for controlling a carbon dioxide hydrogenation reactor as claimed in claim 8 or 9, characterized in that the inlet material temperature of each stage of the carbon dioxide hydrogenation reactor except the final stage is adjusted within the range of 30-65 ℃, preferably 35-56 ℃.
11. The control method of the carbo-hydrogenation reactor as recited in claim 10, characterized in that the adjustment rate of the inlet material temperature of each stage of the carbo-hydrogenation reactor except the last stage is in the range of 0.5-10 ℃/hr, preferably 2.0-6.0 ℃/hr.
12. The method for controlling a carbohydrogenation reactor as recited in claim 8 or 9, wherein the adjustment range of the hydrogen acetylene ratio of each of the carbon hydrogenation reactors except the last bed is 0.5 to 4.0, preferably 0.8 to 3.6.
13. The method as set forth in claim 12, wherein the adjustment rate of the hydrogen acetylene ratio of the carbon hydrogenation reactor for each stage other than the last stage is in the range of 0.01 to 0.4/hr, preferably 0.04 to 0.2/hr.
14. The method for controlling a carbon dioxide hydrogenation reactor as claimed in claim 1, wherein the multi-stage bed carbon dioxide hydrogenation reactor inlet stream comprises at least ethylene, ethane and acetylene;
the inlet material of the multi-stage bed carbon dioxide hydrogenation reactor also comprises at least one of hydrogen, methane, propylene and propane;
the volume content of acetylene in the inlet material of the multi-section bed hydrogenation reactor is at least more than 0.25 percent and less than 5.6 percent.
15. A method for refining ethylene and removing acetylene by hydrogenation is applied to a separation process of an ethylene cracking device, wherein the separation process comprises a sequential separation process, a front-end depropanization and rear-end hydrogenation process and a front-end deethanization and rear-end hydrogenation process, and is characterized in that the control method of any one of claims 1 to 14 is used.
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