CN109248542B - Method and system for determining optimal adsorption time of pressure swing adsorption device - Google Patents
Method and system for determining optimal adsorption time of pressure swing adsorption device Download PDFInfo
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Abstract
The invention provides a method and a system for determining the optimal adsorption time of a pressure swing adsorption device, wherein the method comprises the following steps: establishing a mathematical simulation model of the pressure swing adsorption device; carrying out mathematical solution on the established mathematical simulation model; judging whether the product hydrogen composition and the flow in the solving result meet the preset calculation requirement, and if not, correcting the initial value of the adsorption balance kinetic parameter; if the preset calculation requirement is met, establishing a nonlinear programming model of the pressure swing adsorption device, solving the established nonlinear programming model, judging whether an exit condition is met, if so, exiting the solving process, and taking the adsorption time obtained at the moment as the optimal adsorption time of the pressure swing adsorption device; and otherwise, modifying the adsorption time variable in the nonlinear programming model, and continuously solving. The invention can determine the optimal adsorption time of the pressure swing adsorption device on the premise of ensuring the hydrogen recovery quality, efficiency and no pollution of the adsorbent.
Description
Technical Field
The invention relates to the technical field of gas adsorption, in particular to a method and a system for determining the optimal adsorption time of a pressure swing adsorption device.
Background
Pressure swing adsorption is the most important means for obtaining high-purity hydrogen in refineries,the principle of 'adsorption under high pressure and desorption under low pressure' of impurity components in hydrogen-containing material flow is mainly utilized for hydrogen enrichment. The pressure swing adsorption tower is a composite bed layer of various adsorbents, usually, activated alumina, silica gel, activated carbon and various molecular sieve adsorbents are filled in sequence from the bottom to the top of the tower, and the filling types and proportions of the various adsorbents are slightly different according to different raw materials to be treated, wherein the alumina adsorbent is used for H2O、H2S and other components have good adsorption effect, and silica gel is easy to adsorb H2O、CO2Heavy hydrocarbon impurities, activated carbon to CO2And various hydrocarbon impurities are better adsorbed, and various molecular sieve adsorbents are used for adsorbing and separating specific components, such as CO special adsorbent, carbon molecular sieve adsorbent and the like.
In actual production, the adsorption pressure, the regeneration desorption pressure and the like of the pressure swing adsorption device are matched with an upstream system and a downstream system and are basically constant, and only the adsorption time is an important parameter for operation and adjustment of the device. Under the normal condition, the adsorption time is prolonged, which means that the regeneration frequency in unit time is reduced, the recovery efficiency of the target product hydrogen can be improved, but the overlong adsorption time easily causes impurities to penetrate through a bed layer to cause unqualified product hydrogen quality, and the adsorbent is poisoned under the serious condition; conversely, shortening the adsorption time means that the regeneration frequency per unit time increases, and the hydrogen recovery efficiency decreases. Therefore, for the determined pressure swing adsorption device, the determination and accurate calculation of the optimal adsorption time are the core technology for the operation and operation optimization of the pressure swing adsorption device.
The adsorption time of pressure swing adsorption in actual production is determined mainly by the following two methods:
(1) the operator adjusts the adsorption time according to the experience judgment according to the instrument display of the raw material gas flow, the product flow and the like. Because the manual regulation method mainly depends on the experience of operators, is greatly influenced by human factors, and because the gas flow of the raw material and the composition of the raw material gas frequently fluctuate during the operation of the device, the operators are difficult to timely and accurately regulate the corresponding optimal adsorption time, so that lag or deviation is often caused, and the product yield is lower and the product quality is poorer;
(2) the adsorption time is automatically adjusted based on the flow rate and composition information of the pressure swing adsorption raw gas or product gas. Chinese patent CN1314200A provides an improved pressure swing adsorption device control system, which can automatically adjust and control the adsorption time according to the changes of the raw material gas flow, the raw material gas product content and the product gas flow, so as to achieve the purpose of improving the product yield and quality. Chinese patent CN102527188A provides a method for determining the adsorption time of a pressure swing adsorption device, which has the basic idea of calculating the adsorption time-raw material flow rate relationship curve of the preset reference parameters of the pressure swing adsorption device and the adsorption time-raw material flow rate control curve under the preset operation conditions, calculating the real-time dynamic adsorption point of the pressure swing adsorption device according to the real-time detection data, and adjusting the adsorption time by judging the relationship between the real-time dynamic adsorption point and the two curves. The determination methods of the adsorption time related to the two patents are simply related to the inlet and outlet material flow information of the adsorption tower and the adsorption time, and the relationship between the adsorption time and each adsorbent layer is not deeply investigated, so that the optimal adsorption time cannot be essentially demonstrated and obtained. For example, the adsorption time when the raw material gas components and flow rate of reforming hydrogen concentration pressure swing adsorption, refinery dry gas concentration pressure swing adsorption and other devices or pressure swing adsorption devices change greatly is determined, the adsorption time cannot be simply adjusted only by the product hydrogen yield, the product hydrogen purity or the deviation of a dynamic adsorption point at a certain moment and a design working condition, but the optimal adsorption time is comprehensively determined by considering the factors that an adsorbent in an adsorption tower is not polluted and poisoned by certain components and the like on the premise of ensuring that the product hydrogen quality is qualified and the yield is maximized.
Therefore, how to solve the problems of the prior art and provide a new method and system for determining the optimal adsorption time of the pressure swing adsorption of refinery gas is the research direction of those skilled in the art.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a method and a system for determining the optimal adsorption time of a pressure swing adsorption device, which can determine the optimal adsorption time of the pressure swing adsorption device on the premise of ensuring the hydrogen recovery quality and efficiency and preventing an adsorbent from being polluted, thereby improving the economic benefit of enterprises.
In a first aspect, the present invention provides a method for determining an optimal adsorption time of a pressure swing adsorption apparatus, including:
step S1: dividing the pressure swing adsorption device into different adsorption layers according to different types of adsorbents filled in the pressure swing adsorption device, and establishing a mathematical simulation model of the pressure swing adsorption device by adopting an adsorption equilibrium equation, a mass transfer rate equation and a total mass transfer equilibrium equation;
step S2: setting an initial value of an adsorption equilibrium kinetic parameter of a mathematical simulation model of the pressure swing adsorption device according to the design parameters and the operation parameters of the pressure swing adsorption device;
step S3: performing mathematical solution on a mathematical simulation model of the pressure swing adsorption device to obtain the composition and flow rate of product hydrogen and obtain the time for a preset component gas in the feed gas to penetrate a preset adsorption layer;
step S4: judging whether the product hydrogen composition and the flow in the solving result of the step S3 meet the preset calculation requirement, and if not, correcting the initial value of the adsorption equilibrium kinetic parameter in the step S2; if the preset calculation requirement is met, executing step S5;
step S5: establishing a nonlinear programming model of the pressure swing adsorption device;
step S6: solving a nonlinear programming model of the pressure swing adsorption device; during solving, the adsorption time of the pressure swing adsorption device is taken as an optimization variable, the maximum product hydrogen recovery rate is taken as an objective function value, and the constraint conditions that the product hydrogen purity is greater than or equal to a preset purity value and a preset component gas in a feed gas cannot penetrate through a preset adsorption layer are taken; wherein the initial value of the adsorption time of the pressure swing adsorption unit is set according to the theoretically calculated penetration time;
step S7: judging whether the solution of the step S6 reaches an exit condition, wherein the exit condition is: the total increased adsorption time reaches the preset limit condition or the nonlinear programming optimization objective function value is not improved for two times continuously; if so, exiting the solving process, and taking the adsorption time obtained at the moment as the optimal adsorption time of the pressure swing adsorption device; otherwise, modifying the adsorption time variable in the nonlinear programming model, and returning to the step S6.
Further, the adsorption equilibrium equation in step S1 is:
wherein, thetaiRepresenting the coverage rate of a gas component i on a certain layer of adsorbent in the mixed gas to be adsorbed; piRepresents the partial pressure of the gas component i in the mixed gas to be adsorbed; b isiRepresents the langmuir adsorption constant of gas component i on the layer of adsorbent; b isijRepresents the langmuir adsorption constant of component i on the layer of adsorbent in a binary gas mixture comprising component i and component j; kijRepresenting the degree of influence of component j on the adsorption of component i when a binary gas mixture comprising component i and component j is adsorbed on the layer of adsorbent; ki,mixRepresents the adsorption influence parameter of all gas components in the mixed gas to be adsorbed on the gas component i.
Further, the design parameters of the pressure swing adsorption device in the step S2 include the height, the inner diameter, the loading amount, the type, the pore volume and the specific surface area of the pressure swing adsorption device; the operating parameters of the pressure swing adsorption unit include feed gas flow, composition, and adsorption operating temperature, pressure, and theoretical breakthrough time.
Further, the adsorption equilibrium kinetic parameters of the mathematical simulation model of the pressure swing adsorption device in the step S2 include: diffusion coefficient, mass transfer coefficient, peak number and langmuir adsorption equilibrium constant.
Further, the step S4 of determining whether the product hydrogen composition and the flow rate meet the preset calculation requirements means that determining whether the relative deviation between the product hydrogen composition and the flow rate in the solution result of the step S3 and the product hydrogen composition and the flow rate obtained by the industrial practical device is controlled within 1% to 5%.
In a second aspect, the present invention further provides a system for determining an optimal adsorption time of a pressure swing adsorption apparatus, including:
the first modeling unit is used for dividing the pressure swing adsorption device into different adsorption layers according to different types of adsorbents filled in the pressure swing adsorption device, and establishing a mathematical simulation model of the pressure swing adsorption device by adopting an adsorption equilibrium equation, a mass transfer rate equation and a total mass transfer equilibrium equation;
the initial value setting unit is used for setting an initial value of an adsorption equilibrium kinetic parameter of a mathematical simulation model of the pressure swing adsorption device according to the design parameters and the operation parameters of the pressure swing adsorption device;
the first solving unit is used for carrying out mathematical solving on a mathematical simulation model of the pressure swing adsorption device to obtain the composition and flow rate of product hydrogen and obtain the time for a preset component gas in feed gas to penetrate a preset adsorption layer;
the first judgment unit is used for judging whether the product hydrogen composition and the flow in the solving result of the first solving unit meet the preset calculation requirement or not, and if the preset calculation requirement is not met, correcting the initial value of the adsorption equilibrium kinetic parameter in the initial value setting unit; if the preset calculation requirement is met, executing a second modeling unit;
the second modeling unit is used for establishing a nonlinear programming model of the pressure swing adsorption device;
the second solving unit is used for solving a nonlinear programming model of the pressure swing adsorption device; during solving, the adsorption time of the pressure swing adsorption device is taken as an optimization variable, the maximum product hydrogen recovery rate is taken as an objective function value, and the constraint conditions that the product hydrogen purity is greater than or equal to a preset purity value and a preset component gas in a feed gas cannot penetrate through a preset adsorption layer are taken; wherein the initial value of the adsorption time of the pressure swing adsorption unit is set according to the theoretically calculated penetration time;
a second determining unit, configured to determine whether the solution in the second solving unit reaches an exit condition, where the exit condition is: the total increased adsorption time reaches the preset limit condition or the nonlinear programming optimization objective function value is not improved for two times continuously; if so, exiting the solving process, and taking the adsorption time obtained at the moment as the optimal adsorption time of the pressure swing adsorption device; and if not, modifying the adsorption time variable in the nonlinear programming model, and returning to continue executing the second solving unit.
Further, the adsorption equilibrium equation in the first modeling unit is:
wherein, thetaiRepresenting the coverage rate of a gas component i on a certain layer of adsorbent in the mixed gas to be adsorbed; piRepresents the partial pressure of the gas component i in the mixed gas to be adsorbed; b isiRepresents the langmuir adsorption constant of gas component i on the layer of adsorbent; b isijRepresents the langmuir adsorption constant of component i on the layer of adsorbent in a binary gas mixture comprising component i and component j; kijRepresenting the degree of influence of component j on the adsorption of component i when a binary gas mixture comprising component i and component j is adsorbed on the layer of adsorbent; ki,mixRepresents the adsorption influence parameter of all gas components in the mixed gas to be adsorbed on the gas component i.
Further, the design parameters of the pressure swing adsorption device in the initial value setting unit comprise the height and the inner diameter of the pressure swing adsorption device, the filling amount, the type, the pore volume and the specific surface area of the adsorbent; the operating parameters of the pressure swing adsorption unit include feed gas flow, composition, and adsorption operating temperature, pressure, and theoretical breakthrough time.
Further, the adsorption equilibrium kinetic parameters of the mathematical simulation model of the pressure swing adsorption apparatus in the initial value setting unit include: diffusion coefficient, mass transfer coefficient, peak number and langmuir adsorption equilibrium constant.
Further, the first judging unit judges whether the product hydrogen composition and the flow meet the preset calculation requirement or not, and judges whether the relative deviation between the product hydrogen composition and the flow in the solving result of the first solving unit and the product hydrogen composition and the flow obtained by the industrial practical device is controlled within 1% -5%.
According to the technical scheme, the method and the system for determining the optimal adsorption time of the pressure swing adsorption device comprehensively obtain the optimal adsorption time of the pressure swing adsorption device on the premise of ensuring qualified product hydrogen quality, maximized yield, no pollution and poisoning of the adsorbent in the adsorption device by certain components and other factors, so that the operation level of the pressure swing adsorption device can be effectively improved, the operation period of the adsorbent can be effectively prolonged on the premise of ensuring the hydrogen recovery quality, efficiency and no pollution of the adsorbent, and the economic benefit of enterprises is improved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 is a flow chart of a method for determining an optimal adsorption time for a pressure swing adsorption apparatus according to an embodiment of the present invention;
FIG. 2 is a schematic diagram of an optimal adsorption time determination system of a pressure swing adsorption apparatus according to another embodiment of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
An embodiment of the present invention provides a method for determining an optimal adsorption time of a pressure swing adsorption apparatus, referring to a flowchart shown in fig. 1, the method includes the following steps:
step 101: according to different types of adsorbents filled in the pressure swing adsorption device, the pressure swing adsorption device is divided into different adsorption layers, and a mathematical simulation model of the pressure swing adsorption device is established by adopting an adsorption equilibrium equation, a mass transfer rate equation and a total mass transfer equilibrium equation.
In this step, the pressure swing adsorption device mainly refers to a pressure swing adsorption device which takes one or more of reformed hydrogen, refinery low-grade gas, refinery hydrogen-containing dry gas and steam cracking hydrogen production conversion gas as raw materials.
In this step, a mathematical simulation model of the pressure swing adsorption apparatus is established using an adsorption equilibrium equation, a mass transfer rate equation, and a total mass transfer equilibrium equation. It is understood that, in this step, establishing a mathematical simulation model of the pressure swing adsorption apparatus using the adsorption equilibrium equation, the mass transfer rate equation, and the total mass transfer equilibrium equation means establishing a mathematical simulation model of each adsorption layer in the pressure swing adsorption apparatus using the adsorption equilibrium equation, the mass transfer rate equation, and the total mass transfer equilibrium equation, respectively. Wherein, the calculation result of the raw material gas passing through a certain adsorption layer is used as the inlet initial value of the next adsorption layer simulation calculation.
Specifically, assuming constant pressure and temperature, the flow model adopts an axial dispersion piston flow model, the flow rate change caused by adsorption is calculated by a total mass transfer equilibrium equation, the mass transfer rate equation adopts a linear driving force model (LDF), and the adsorption equilibrium equation is described by an improved Langmuir model.
In this step, each model equation is as follows:
mass transfer equilibrium equation of gas component i in infinitesimal volume:
wherein D isLRepresents the bed axial diffusion coefficient, m2/s；CiRepresents the total gas phase concentration of component i, mol/m3(ii) a v represents the air flow velocity, m/s; rhoPDenotes the gas phase density in kg/m at the adsorption pressure P3(ii) a Epsilon represents the porosity of the molecular adsorption bed and is dimensionless;
represents the adsorption equilibrium concentration of the component i, mol/kg.
The total mass transfer equilibrium equation:
wherein C represents the gas phase concentration of the bed layer, mol/m3(ii) a The other parameters are as defined above.
Mass transfer rate equation:
wherein k isiRepresents the gas-solid mass transfer coefficient, s;
represents the gas phase concentration of an adsorption bed of the component i, and mol/kg;
represents the adsorption equilibrium concentration of the component i, mol/kg.
During specific calculation, an adsorption tower bed layer (a pressure swing adsorption device) is divided into different micro-element sections from the bottom to the top of the tower according to different types of adsorbents (according to actual calculation requirements, the same adsorbent layer can also be divided into a plurality of micro-element sections), a calculation result of an outlet of each micro-element section is used as an initial calculation value of a next micro-element section inlet and is sequentially calculated to the top of the adsorption tower, and if the deviation between the calculation result of the top of the adsorption tower and the actual value is larger, the calculation result is returned to the first micro-element section at the bottom of the tower, and corresponding parameters are modified and adjusted. Each infinitesimal section is modeled and solved simultaneously by adopting the control equations. The adsorption quantity of different components passing through the adsorbent is calculated by an adsorption equilibrium equation, the time of the component passing through the micro-element section is calculated by a mass transfer rate equation, and a mass transfer material equilibrium equation (a total mass transfer material equation and a single-component material equation) mainly calculates the properties (concentration, flow and the like) of the component at the outlet of the micro-element section by describing a material equilibrium relation of the component entering and exiting the micro-element section.
Wherein, the adsorption equilibrium equation is:
wherein, thetaiRepresenting the coverage rate of a gas component i on a certain layer of adsorbent in the mixed gas to be adsorbed; piDenotes the partial pressure of the gas component i in the gas mixture to be adsorbed, 106Pa；BiShows the Langmuir adsorption constant of gas component i on the adsorbent of the layer, 106Pa-1；BijRepresents the langmuir adsorption constant of component i on the layer of adsorbent in a binary gas mixture comprising component i and component j; kijRepresenting the degree of influence of component j on the adsorption of component i when a binary gas mixture comprising component i and component j is adsorbed on the layer of adsorbent; ki,mixMeans all of the gas mixture to be adsorbedThe adsorption of the gas component on the gas component i influences the parameters.
It should be noted that the adsorption equilibrium equation used in this embodiment is based on the modified langmuir model. The following is an introduction of the improved langmuir model:
in the current field of adsorption separation, single-component langmuir models or extended langmuir models are mainly used to describe the phase equilibrium problem of the adsorption process. On one hand, the single-component Langmuir model is suitable for researching the adsorption process of single-component gas, does not consider the mutual influence among different components, and cannot describe the adsorption process of multi-component gas mixture; on the other hand, the expanded langmuir model is a model widely applied in recent years for describing a multi-component gas-solid adsorption process, theoretically, adsorption equilibrium constants of various components in a mixed atmosphere on an adsorbent need to be determined through experiments and then calculated, but because the gas adsorption equilibrium constants of more than two components are extremely difficult to obtain, when the model is actually applied, the single-component langmuir adsorption constant of the component is still adopted to replace the adsorption equilibrium constant of the component in a mixed gas, and the inaccuracy of calculation of the equilibrium adsorption amount of the mixed gas is certainly increased through the simplified treatment. In response to this technical problem, the present embodiment provides an improved langmuir model, which can accurately determine the adsorption amount of the multi-component adsorption process.
The establishment process of the adsorption equilibrium equation provided in this embodiment is given below:
a. through experimental means or data retrieval, single-component Langmuir models of each gas component in the mixed gas to be measured on the same adsorbent S are respectively obtained, and the single-component Langmuir adsorption constant B of each gas component is obtainedi(ii) a Wherein the mixed gas to be measured contains n gas components, i is more than or equal to 1 and less than or equal to n.
b. According to the gas composition of the mixed gas to be measured, preparing the gas of each two components into a binary gas mixture, and co-preparing to obtain the gas mixture
A group of binary gas mixtures; it is composed ofIn formulating each of the two component gases into a binary gas mixture, the molar ratio of the two component gases in the binary gas mixture may be any molar ratio, preferably the molar ratio of the two gas components is 1: 1.
c. Respectively acquiring the Langmuir adsorption constant B of each gas component in each group of binary gas mixtures on the adsorbentijWherein B isijRepresents the langmuir adsorption constant of component i on said adsorbent S in a binary gas mixture comprising component i and component j; this step can be obtained experimentally.
d. Respectively obtaining a binary interaction parameter K among the gas components in each group of binary gas mixtureijWherein, K isij＝Bij/Bi，KijRepresents the degree of influence of component j on the adsorption of component i when a binary gas mixture comprising component i and component j is adsorbed on the adsorbent S; wherein, if 0 < KijIf the value is less than 1, the gas component j has an inhibiting effect on the adsorption process of the gas component i; if Kij1 means that the gas component j has no influence or little influence on the adsorption process of the gas component i; when i ═ j, Kij1 is ═ 1; if KijAnd > 1, the gas component j has the promotion effect on the adsorption process of the gas component i. Wherein, KijCloser to 1, meaning less influence of the component, KijA larger deviation of 1 indicates a stronger influence of the composition.
e. D, obtaining a binary interaction parameter K among the gas components in the binary gas mixture according to the step dijObtaining the adsorption parameter K of all gas components in the mixed gas to be measured on the gas component ii,mix(ii) a In this step, the adsorption parameter K of all gas components in the mixed gas to be measured on the gas component i is obtained in the following manneri,mix：
Wherein, yjShows the influence of the adsorption of the gas component j on the gas component iSection factor, yjIs the gas volume proportion of the gas component j in the gas mixture to be measured.
f. According to the adsorption parameter K of all gas components in the mixed gas to be measured on the gas component ii,mixEstablishing a gas-solid adsorption equilibrium equation of the mixed gas to be measured:
wherein, thetaiDenotes the coverage of gas component i on the adsorbent in the gas mixture to be determined, PiRepresenting the partial pressure of gas component i in the gas mixture to be measured, 106Pa，BiDenotes the Langmuir adsorption constant of gas component i on the adsorbent, 106Pa-1；。
g. The equation is solved and the adsorption amount of each gas component on the adsorbent S is obtained.
Step 102: and setting an initial value of the adsorption equilibrium kinetic parameter of a mathematical simulation model of the pressure swing adsorption device according to the design parameter and the operation parameter of the pressure swing adsorption device.
In this step, the design parameters of the pressure swing adsorption device include the height and inner diameter of the pressure swing adsorption device, and the filling amount, type, pore volume and specific surface area of the adsorbent; the operating parameters of the pressure swing adsorption unit include feed gas flow, composition, and adsorption operating temperature, pressure, and theoretical breakthrough time. The adsorption equilibrium kinetic parameters of the mathematical simulation model of the pressure swing adsorption unit include: diffusion coefficient, mass transfer coefficient, peak number and langmuir adsorption equilibrium constant.
Step 103: and carrying out mathematical solution on the mathematical simulation model of the pressure swing adsorption device to obtain the composition and flow of the product hydrogen and obtain the time for the preset component gas in the feed gas to penetrate through the preset adsorption layer.
In this step, when the mathematical simulation model of the pressure swing adsorption apparatus is mathematically solved, the time for the gas with the predetermined composition in the feed gas to penetrate through the predetermined adsorption layer needs to be obtained, so as to provide a basis for part of the constraint conditions in the subsequent step 106.
For example, it is assumed that the design parameters and the operation parameters of a certain pressure swing adsorption apparatus (adsorption column) are as shown in tables 1 and 2 below. Table 3 shows the feed gas, product hydrogen, and stripping gas data. The breakthrough time to be achieved for this adsorption column then mainly relates to H2Penetration time of O through alumina bed layer and finally through silica gel layer, C2+ penetration time of hydrocarbons through alumina layer, silica gel layer and finally through activated carbon layer, CH4And finally penetrating through the molecular sieve layer through the alumina layer, the silica gel layer and the activated carbon layer.
TABLE 1 adsorption column part design parameters
TABLE 2 adsorption column operating parameters
| Item | Content providing method and apparatus |
| Adsorption pressure, MPa | 2.1 |
| Temperature of raw material at DEG C | 30～40 |
| Process flow | VPSA，6-2-3 |
| Single column adsorption time, s | 210 |
TABLE 3 pressure swing adsorption plant stream information
Step 104: judging whether the product hydrogen composition and the flow in the solving result of the step 103 meet the preset calculation requirement, and if not, correcting the initial value of the adsorption balance kinetic parameter in the step 102; if the predetermined calculation requirement is satisfied, go to step 105.
In this step, the judgment of whether the product hydrogen composition and the flow rate meet the preset calculation requirements means that whether the relative deviation between the product hydrogen composition and the flow rate in the solution result of step 103 and the product hydrogen composition and the flow rate obtained by the industrial practical device is controlled within 1% -5%.
When the product hydrogen composition and flow in the solution of step 103 do not meet the preset calculation requirements, the adsorption equilibrium kinetic parameters in step 102 may be corrected based on actual industrial operating data.
Step 105: and establishing a nonlinear programming model of the pressure swing adsorption device.
Step 106: solving a nonlinear programming model of the pressure swing adsorption device; during solving, the adsorption time of the pressure swing adsorption device is taken as an optimization variable, the maximum product hydrogen recovery rate is taken as an objective function value, and the constraint conditions that the product hydrogen purity is greater than or equal to a preset purity value and a preset component gas in a feed gas cannot penetrate through a preset adsorption layer are taken; wherein the initial value of the adsorption time of the pressure swing adsorption unit is set according to the theoretically calculated breakthrough time.
In this step, the product hydrogen recovery is defined as the ratio of the flow of pure hydrogen in the product to the flow of pure hydrogen in the feed. In this step, the preset purity value in the preset condition is preferably 99.9%. In this step, in order to ensure that the adsorption layer of the pressure swing adsorption apparatus is free from contamination, it is also necessary to set, in the constraint condition, that the predetermined component gas in the raw material gas cannot penetrate the predetermined adsorption layer. For example, for the feed gases andthe adsorption tower can be used for stipulating: h2O does not penetrate the silica gel bed, i.e. tAdsorption＜tH2O，C2+ heavy hydrocarbons not penetrating the bed of activated carbon, i.e. tAdsorption＜tC2+，CH4Without penetrating the molecular sieve bed, i.e. tAdsorption＜tCH4。
Since the solving process of the nonlinear programming model can be realized by a special solver, which belongs to the prior art, the details are not described here.
Step 107: judging whether the solution of step 106 reaches an exit condition, wherein the exit condition is: the total increased adsorption time reaches the preset limit condition or the nonlinear programming optimization objective function value is not improved for two times continuously; if so, exiting the solving process, and taking the adsorption time obtained at the moment as the optimal adsorption time of the pressure swing adsorption device; otherwise, modifying the adsorption time variable in the nonlinear programming model, and returning to the step 106.
In this step, it is necessary to determine whether the solution of step 106 reaches an exit condition. Here, the exit condition means: the total adsorption time is increased to a preset limit. For example, the preset restriction condition is that the total increase time is ≦ 25 s. And when the total increased adsorption time reaches 25s, meeting an exit condition, exiting the solving process, and taking the obtained adsorption time as the optimal adsorption time of the pressure swing adsorption device. In addition, when the nonlinear programming optimization objective function value is not improved for two times, the solving process is also exited no matter whether the total increased adsorption time reaches the preset limit condition or not. And when the solution of the step 106 does not reach the exit condition, continuing to perform the optimal solution by modifying the adsorption time variable in the nonlinear programming model. For example, the adsorption time is increased by 0.5-5% or a fixed value, such as 5s, based on the initial value of the adsorption time, and the optimization solution is continued until the exit condition is satisfied.
For example, the optimization results obtained by the method of the present embodiment are shown in table 4, and it can be seen that the adsorption time is increased from 210s to 218s, the hydrogen recovery rate is increased from 77.79% to 83.01%, and no H is caused compared with the current operation condition2O penetrating the silica gel layer, C2 +Heavy hydrocarbons not penetrating the activated carbon layer, CH4Is also within the control index.
TABLE 4 optimization results
| The invention calculates the result | Results of original working conditions | |
| Adsorption time, s | 218 | 210 |
| Hydrogen recovery rate% | 83.01 | 77.79 |
The optimum adsorption time determination method provided by the present invention will be described below by way of another specific example.
Wherein, tables 5 and 6 are the original design parameters and operation parameters of the shift gas stripping concentration pressure swing adsorption device of a certain refinery steam cracking hydrogen production device, and table 7 is the material inlet and outlet information of the pressure swing adsorption device. Due to enterprise process flow adjustments, a stream containing hydrogen is scheduled to be sent to the pressure swing adsorption unit, and table 8 is the stream information.
A mathematical simulation model and a nonlinear programming model of the pressure swing adsorption device are established according to the steps shown in FIG. 1, and the maximum total increase time of the adsorption time in the nonlinear programming model is set to be 15 s. And then entering an iterative solution process until the condition is met and exiting.
The final optimization results are shown in table 9, and it can be seen that compared with the current operation condition, the adsorption time is reduced from 225s to 221s, the hydrogen recovery rate is reduced from 88.48% to 88.31%, and no H is caused2O penetrating the silica gel layer, C2 +Heavy hydrocarbons not penetrating the activated carbon layer, CH4Is also within the control index. If the adsorption time is not decreased, C is easily caused2 +Heavy hydrocarbons penetrate the activated carbon layer causing poisoning of the molecular sieve adsorbent. It can be understood that, compared with the current operating condition, the longer the adsorption time is, the better the adsorption time is, but the recovery quality and the recovery efficiency of the product hydrogen and whether the adsorbent is polluted need to be considered at the same time.
TABLE 5 adsorption column part design parameters
TABLE 6 adsorption column operating parameters
| Item | Content providing method and apparatus |
| Adsorption pressure, MPa | 2.1 |
| Temperature of raw material at DEG C | 30～40 |
| Process flow | 10-1-6 |
| Single column adsorption time, s | 225 |
TABLE 7 pressure swing adsorption plant stream information
Table 8 hydrogen containing stream information
| Hydrogen containing stream | |
| Flow rate, Nm3/h | 11340 |
| Composition, is% | |
| H2 | 75.49 |
| N2 | 0 |
| CH4 | 15.87 |
| C2H6 | 2.98 |
| C3H8 | 2.56 |
| C4H10 | 3.10 |
| H2O | 0 |
| H2S | 30ppm |
| ∑ | 100 |
TABLE 9 optimization results
| The invention calculates the result | Results of original working conditions | |
| Adsorption time, s | 221 | 225 |
| Hydrogen recovery rate% | 88.31 | 88.48 |
According to the technical scheme, the method for determining the optimal adsorption time of the pressure swing adsorption device provided by the embodiment of the invention comprehensively obtains the optimal adsorption time of the pressure swing adsorption device on the premise of ensuring qualified product hydrogen quality, maximized yield, no pollution and poisoning of the adsorbent in the adsorption device by certain components and other factors, so that the operation level of the pressure swing adsorption device can be effectively improved, the operation period of the adsorbent can be effectively prolonged on the premise of ensuring the hydrogen recovery quality, efficiency and no pollution of the adsorbent, and the economic benefit of enterprises can be improved.
Another embodiment of the present invention further provides a system for determining an optimal adsorption time of a pressure swing adsorption apparatus, referring to fig. 2, the system comprising: a first modeling unit 21, an initial value setting unit 22, a first solving unit 23, a first judging unit 24, a second modeling unit 25, a second solving unit 26, and a second judging unit 27, wherein:
the first modeling unit 21 is used for dividing the pressure swing adsorption device into different adsorption layers according to different types of adsorbents filled in the pressure swing adsorption device, and establishing a mathematical simulation model of the pressure swing adsorption device by adopting an adsorption equilibrium equation, a mass transfer rate equation and a total mass transfer equilibrium equation;
an initial value setting unit 22, configured to set an initial value of an adsorption equilibrium kinetic parameter of a mathematical simulation model of the pressure swing adsorption apparatus according to design parameters and operating parameters of the pressure swing adsorption apparatus;
the first solving unit 23 is configured to perform mathematical solving on the mathematical simulation model of the pressure swing adsorption apparatus, obtain the product hydrogen composition and flow rate, and obtain the time for a predetermined component gas in the feed gas to penetrate through a predetermined adsorption layer;
the first judging unit 24 is configured to judge whether the product hydrogen composition and the flow rate in the solution result of the first solving unit meet preset calculation requirements, and if the preset calculation requirements are not met, modify the initial value of the adsorption equilibrium kinetic parameter in the initial value setting unit; if the preset calculation requirement is met, executing a second modeling unit;
the second modeling unit 25 is used for establishing a nonlinear programming model of the pressure swing adsorption device;
the second solving unit 26 is used for solving a nonlinear programming model of the pressure swing adsorption device; during solving, the adsorption time of the pressure swing adsorption device is taken as an optimization variable, the maximum product hydrogen recovery rate is taken as an objective function value, and the constraint conditions that the product hydrogen purity is greater than or equal to a preset purity value and a preset component gas in a feed gas cannot penetrate through a preset adsorption layer are taken; wherein the initial value of the adsorption time of the pressure swing adsorption unit is set according to the theoretically calculated penetration time;
a second determining unit 27, configured to determine whether the solution in the second solving unit reaches an exit condition, where the exit condition is: the total increased adsorption time reaches the preset limit condition or the nonlinear programming optimization objective function value is not improved for two times continuously; if so, exiting the solving process, and taking the adsorption time obtained at the moment as the optimal adsorption time of the pressure swing adsorption device; and if not, modifying the adsorption time variable in the nonlinear programming model, and returning to continue executing the second solving unit.
In an alternative embodiment, the adsorption equilibrium equation in the first modeling unit 21 is:
wherein, thetaiRepresenting the coverage rate of a gas component i on a certain layer of adsorbent in the mixed gas to be adsorbed; piTo representPartial pressure of gas component i in the mixed gas to be adsorbed; b isiRepresents the langmuir adsorption constant of gas component i on the layer of adsorbent; b isijRepresents the langmuir adsorption constant of component i on the layer of adsorbent in a binary gas mixture comprising component i and component j; kijRepresenting the degree of influence of component j on the adsorption of component i when a binary gas mixture comprising component i and component j is adsorbed on the layer of adsorbent; ki,mixRepresents the adsorption influence parameter of all gas components in the mixed gas to be adsorbed on the gas component i.
In an alternative embodiment, the design parameters of the pressure swing adsorption device in the initial value setting unit 22 include the height, inner diameter, and adsorbent packing amount, type, pore volume, and specific surface area of the pressure swing adsorption device; the operating parameters of the pressure swing adsorption unit include feed gas flow, composition, and adsorption operating temperature, pressure, and theoretical breakthrough time.
In an alternative embodiment, the adsorption equilibrium kinetic parameters of the mathematical simulation model of the pressure swing adsorption apparatus in the initial value setting unit 22 include: diffusion coefficient, mass transfer coefficient, peak number and langmuir adsorption equilibrium constant.
In an alternative embodiment, the first judging unit 24 judges whether the product hydrogen composition and the flow rate meet the preset calculation requirement, and judges whether the relative deviation between the product hydrogen composition and the flow rate in the solution result of the first solving unit 23 and the product hydrogen composition and the flow rate obtained by the industrial practical device is controlled within 1% -5%.
The system for determining the optimal adsorption time of the pressure swing adsorption device according to the embodiment of the present invention can be used for executing the method for determining the optimal adsorption time of the pressure swing adsorption device according to the embodiment, and the principle and the technical effect are similar, and therefore, detailed description is omitted here.
In the description of the present invention, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.
The above examples are only for illustrating the technical solutions of the present invention, and not for limiting the same; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (6)
1. A method for determining the optimal adsorption time of a pressure swing adsorption device is characterized by comprising the following steps:
step S1: dividing the pressure swing adsorption device into different adsorption layers according to different types of adsorbents filled in the pressure swing adsorption device, and establishing a mathematical simulation model of the pressure swing adsorption device by adopting an adsorption equilibrium equation, a mass transfer rate equation and a total mass transfer equilibrium equation;
step S2: setting an initial value of an adsorption equilibrium kinetic parameter of a mathematical simulation model of the pressure swing adsorption device according to the design parameters and the operation parameters of the pressure swing adsorption device;
step S3: performing mathematical solution on a mathematical simulation model of the pressure swing adsorption device to obtain the composition and flow rate of product hydrogen and obtain the time for a preset component gas in the feed gas to penetrate a preset adsorption layer;
step S4: judging whether the product hydrogen composition and the flow in the solving result of the step S3 meet the preset calculation requirement, and if not, correcting the initial value of the adsorption equilibrium kinetic parameter in the step S2; if the preset calculation requirement is met, executing step S5;
step S5: establishing a nonlinear programming model of the pressure swing adsorption device;
step S6: solving a nonlinear programming model of the pressure swing adsorption device; during solving, the adsorption time of the pressure swing adsorption device is taken as an optimization variable, the maximum product hydrogen recovery rate is taken as an objective function value, and the constraint conditions that the product hydrogen purity is greater than or equal to a preset purity value and a preset component gas in a feed gas cannot penetrate through a preset adsorption layer are taken; wherein the initial value of the adsorption time of the pressure swing adsorption unit is set according to the theoretically calculated penetration time;
step S7: judging whether the solution of the step S6 reaches an exit condition, wherein the exit condition is: the total increased adsorption time reaches the preset limit condition or the nonlinear programming optimization objective function value is not improved for two times continuously; if so, exiting the solving process, and taking the adsorption time obtained at the moment as the optimal adsorption time of the pressure swing adsorption device; otherwise, modifying the adsorption time variable in the nonlinear programming model, and returning to the step S6;
wherein the adsorption equilibrium equation in step S1 is:
wherein, thetaiRepresenting the coverage rate of a gas component i on a certain layer of adsorbent in the mixed gas to be adsorbed; piRepresents the partial pressure of the gas component i in the mixed gas to be adsorbed; b isiTo representThe langmuir adsorption constant of gas component i on the layer of adsorbent; b isijRepresents the langmuir adsorption constant of component i on the layer of adsorbent in a binary gas mixture comprising component i and component j; kijRepresenting the degree of influence of component j on the adsorption of component i when a binary gas mixture comprising component i and component j is adsorbed on the layer of adsorbent; ki,mixRepresenting the adsorption influence parameter of all gas components in the mixed gas to be adsorbed on the gas component i;
wherein, the design parameters of the pressure swing adsorption device in the step S2 include the height, the inner diameter, the filling amount, the type, the pore volume and the specific surface area of the pressure swing adsorption device; the operating parameters of the pressure swing adsorption unit include feed gas flow, composition, and adsorption operating temperature, pressure, and theoretical breakthrough time.
2. The method of claim 1, wherein the adsorption equilibrium kinetic parameters of the mathematical simulation model of the pressure swing adsorption apparatus of step S2 include: diffusion coefficient, mass transfer coefficient, peak number and langmuir adsorption equilibrium constant.
3. The method of claim 1, wherein the step S4 of determining whether the product hydrogen composition and flow rate satisfy the predetermined calculation requirements is to determine whether the relative deviation between the product hydrogen composition and flow rate in the solution result of step S3 and the product hydrogen composition and flow rate obtained by the industrial real plant is controlled within 1% -5%.
4. A system for determining an optimum adsorption time for a pressure swing adsorption apparatus, comprising:
the first modeling unit is used for dividing the pressure swing adsorption device into different adsorption layers according to different types of adsorbents filled in the pressure swing adsorption device, and establishing a mathematical simulation model of the pressure swing adsorption device by adopting an adsorption equilibrium equation, a mass transfer rate equation and a total mass transfer equilibrium equation;
the initial value setting unit is used for setting an initial value of an adsorption equilibrium kinetic parameter of a mathematical simulation model of the pressure swing adsorption device according to the design parameters and the operation parameters of the pressure swing adsorption device;
the first solving unit is used for carrying out mathematical solving on a mathematical simulation model of the pressure swing adsorption device to obtain the composition and flow rate of product hydrogen and obtain the time for a preset component gas in feed gas to penetrate a preset adsorption layer;
the first judgment unit is used for judging whether the product hydrogen composition and the flow in the solving result of the first solving unit meet the preset calculation requirement or not, and if the preset calculation requirement is not met, correcting the initial value of the adsorption equilibrium kinetic parameter in the initial value setting unit; if the preset calculation requirement is met, executing a second modeling unit;
the second modeling unit is used for establishing a nonlinear programming model of the pressure swing adsorption device;
the second solving unit is used for solving a nonlinear programming model of the pressure swing adsorption device; during solving, the adsorption time of the pressure swing adsorption device is taken as an optimization variable, the maximum product hydrogen recovery rate is taken as an objective function value, and the constraint conditions that the product hydrogen purity is greater than or equal to a preset purity value and a preset component gas in a feed gas cannot penetrate through a preset adsorption layer are taken; wherein the initial value of the adsorption time of the pressure swing adsorption unit is set according to the theoretically calculated penetration time;
a second determining unit, configured to determine whether the solution in the second solving unit reaches an exit condition, where the exit condition is: the total increased adsorption time reaches the preset limit condition or the nonlinear programming optimization objective function value is not improved for two times continuously; if so, exiting the solving process, and taking the adsorption time obtained at the moment as the optimal adsorption time of the pressure swing adsorption device; otherwise, modifying the adsorption time variable in the nonlinear programming model, and returning to continue executing the second solving unit, wherein the adsorption equilibrium equation in the first modeling unit is as follows:
wherein, thetaiRepresenting the coverage rate of a gas component i on a certain layer of adsorbent in the mixed gas to be adsorbed; piRepresents the partial pressure of the gas component i in the mixed gas to be adsorbed; b isiRepresents the langmuir adsorption constant of gas component i on the layer of adsorbent; b isijRepresents the langmuir adsorption constant of component i on the layer of adsorbent in a binary gas mixture comprising component i and component j; kijRepresenting the degree of influence of component j on the adsorption of component i when a binary gas mixture comprising component i and component j is adsorbed on the layer of adsorbent; ki,mixRepresenting the adsorption influence parameter of all gas components in the mixed gas to be adsorbed on the gas component i;
the design parameters of the pressure swing adsorption device in the initial value setting unit comprise the height and the inner diameter of the pressure swing adsorption device, the filling amount, the category, the pore volume and the specific surface area of an adsorbent; the operating parameters of the pressure swing adsorption unit include feed gas flow, composition, and adsorption operating temperature, pressure, and theoretical breakthrough time.
5. The system of claim 4, wherein the adsorption equilibrium kinetic parameters of the mathematical simulation model of the pressure swing adsorption unit in the initial value setting unit comprise: diffusion coefficient, mass transfer coefficient, peak number and langmuir adsorption equilibrium constant.
6. The system according to claim 4, wherein the first judging unit judges whether the product hydrogen composition and the flow rate meet the preset calculation requirements or not by judging whether the relative deviation between the product hydrogen composition and the flow rate in the solving result of the first solving unit and the product hydrogen composition and the flow rate obtained by the industrial practical device is controlled within 1-5%.
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