CN109248542A - The optimal adsorption time of pressure-swing absorption apparatus determines method and system - Google Patents
The optimal adsorption time of pressure-swing absorption apparatus determines method and system Download PDFInfo
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Abstract
The present invention provides a kind of optimal adsorption times of pressure-swing absorption apparatus to determine method and system, which comprises establishes the mathematical simulation model of pressure-swing absorption apparatus；Mathematical is carried out to mathematical simulation model is established；Judge whether product hydrogen composition and flow in solving result meet default calculate and require, if not meeting pre-designed calculation requirement, corrects adsorption equilibrium kinetic parameter initial value；If meeting default calculate to require, then establish the Nonlinear programming Model of the pressure-swing absorption apparatus, and the Nonlinear programming Model of foundation is solved, judge whether to reach exit criteria, if, solution procedure is then exited, and using the adsorption time obtained at this time as the optimal adsorption time of the pressure-swing absorption apparatus；Otherwise, the adsorption time variable in the Nonlinear programming Model is modified, and continues to solve.The present invention can determine the optimal adsorption time of pressure-swing absorption apparatus under the premise of ensuring hydrogen recycling quality, efficiency and not contaminated adsorbent.
Description
Technical field
The present invention relates to gas-adsorption technique fields, and in particular to a kind of optimal adsorption time determination side of pressure-swing absorption apparatus
Method and system.
Background technique
Pressure-variable adsorption is the main means that refinery obtains High Purity Hydrogen, mainly utilizes impurity composition " high pressure in hydrogeneous logistics
Lower absorption desorbs under low pressure " principle carry out hydrogen-rich.Pressure-variable adsorption adsorption tower is the composite bed of a variety of adsorbents, is led to
In normal situation, activated alumina, silica gel, active carbon, various types of adsorbent of molecular sieve, root are successively loaded from tower bottom to tower top
Different according to the raw material of processing, the type and ratio of various adsorbent fillings slightly have difference, wherein alumina type adsorbent is to H2O、
H2The components such as S have good suction-operated, and silica gel easily adsorbs H2O、CO2, heavy hydrocarbons impurity, active carbon is to CO2, various hydro carbons
Impurity absorption is preferable, and various types of adsorbent of molecular sieve are the adsorbing separations for specific components, as CO Special adsorbent,
Carbon molecular sieve adsorbent etc..
In actual production, the adsorptive pressure of pressure-swing absorption apparatus, regeneration desorption pressures etc. match with upstream and downstream system,
Substantially invariable, only adsorption time is the important parameter that device operation is adjusted.Under normal conditions, when extending absorption
Between, it is meant that regeneration frequency is reduced in the unit time, the recovery efficiency of purpose product hydrogen can be improved, but adsorption time is too long easily
Causing impurity to penetrate bed keeps product hydrogen off quality, causes adsorbent to be poisoned under serious conditions；Conversely, when shortening absorption
Between, it is meant that regeneration frequency increases in the unit time, then reduces hydrogen recovery efficiency.Therefore determining pressure-variable adsorption is filled
It sets, the determination of optimal adsorption time and accurately calculating are the core technologies of pressure-swing absorption apparatus operation, operation optimization.
The adsorption time determination of pressure-variable adsorption mainly has following two categories method in actual production:
(1) operative employee shows according to instrument such as raw gas flow, product flows, and empirically judgement carries out adsorption time
Adjustment.Since method of manual adjustment relies primarily on operative employee's experience, be affected by human factors it is larger, and because device run Central Plains
Expect throughput, unstripped gas product form frequent fluctuation, operative employee is difficult the tune of the corresponding optimal adsorption time of progress promptly and accurately
It is whole, lag or deviation are often resulted in, also allows for that product yield is lower, product quality is poor；
(2) based on pressure-variable adsorption unstripped gas or product throughput, the adsorption time automatic adjustment for forming information.Chinese patent
CN1314200A provides a kind of improved pressure-swing absorption apparatus control system, can be contained according to raw gas flow, unstripped gas product
The variation auto-adjustment control adsorption time of amount and product throughput achievees the purpose that improve product yield and quality.It is Chinese special
Sharp CN102527188A provides a kind of determination method of adsorption time of variable pressure adsorption plant, and basic thought is to calculate separately transformation
Adsorption time-raw material under the adsorption time of adsorbent equipment preset reference parameter-raw material flow relation curve, preset operating condition
Flow control curve, then the real-time Dynamic Adsorption point of pressure-swing absorption apparatus is calculated by real-time detector data, by judging dynamic in real time
Relationship of the absorption point with above two curve, and then adjust adsorption time.The determination side for the adsorption time that above-mentioned two patent is related to
Method is simply associated with adsorption tower disengaging logistics information with adsorption time, does not investigate adsorption time and each adsorbent layer deeply
Relationship, cannot substantially prove, obtain optimal adsorption time.Such as reform hydrogen concentrate pressure-variable adsorption, the change of oil refinery dry gas concentrate
The adsorption time when devices such as pressure absorption or larger pressure-swing absorption apparatus feed gas composition, changes in flow rate is determining, cannot be simple
Adsorption time is only adjusted with the deviation of product hydrogen yield, product hydrogen purity or certain moment Dynamic Adsorption point and design conditions, and
It is that also need to consider that adsorbent is not by certain groups in adsorption tower under the premise of guaranteeing that product hydrogen is up-to-standard, yield maximizes
Divide the factors such as pollution poisoning, it is comprehensive to determine optimal adsorption time.
Therefore, how prior art problem to be solved, when a kind of optimal absorption of new refinery gas pressure-variable adsorption is provided
Between the method and system that determine, where the research direction of as those skilled in the art.
Summary of the invention
For the defects in the prior art, the present invention provide a kind of optimal adsorption time of pressure-swing absorption apparatus determine method and
System, the present invention can determine pressure-variable adsorption under the premise of ensuring hydrogen recycling quality, efficiency and not contaminated adsorbent
The optimal adsorption time of device, to improve Business Economic Benefit.
In a first aspect, the present invention provides a kind of optimal adsorption times of pressure-swing absorption apparatus to determine method, comprising:
Step S1: the difference of adsorbent classification is loaded according to pressure-swing absorption apparatus, pressure-swing absorption apparatus is divided into difference
Adsorption layer establish the pressure-swing absorption apparatus and using absorbing balance equation, mass transfer rate equation and total mass transfer equilibrium equation
Mathematical simulation model；
Step S2: according to the design parameter and operating parameter of the pressure-swing absorption apparatus, the pressure-swing absorption apparatus is set
Mathematical simulation model adsorption equilibrium kinetic parameter initial value；
Step S3: carrying out Mathematical to the mathematical simulation model of the pressure-swing absorption apparatus, obtain product hydrogen composition and
Flow, while obtaining the time that predetermined component gas in unstripped gas penetrates predetermined adsorption layer；
Step S4: whether product hydrogen composition and flow in judgment step S3 solving result, which meet default calculate, requires, if
Pre-designed calculation requirement is not met, then the adsorption equilibrium kinetic parameter initial value in amendment step S2；If meeting default calculate to want
It asks, thens follow the steps S5；
Step S5: the Nonlinear programming Model of the pressure-swing absorption apparatus is established；
Step S6: the Nonlinear programming Model of the pressure-swing absorption apparatus is solved；When solving, with the transformation
The adsorption time of adsorbent equipment is optimized variable, to maximize product hydrogen retrieval rate as target function value, with product hydrogen hydrogen purity
It is constraint condition that predetermined adsorption layer, which cannot be penetrated, more than or equal to predetermined component gas in default Reinheitszahl and unstripped gas；Its
In, the initial value of the adsorption time of the pressure-swing absorption apparatus is configured according to the time of break-through of theoretical calculation；
Step S7: whether the solution of judgment step S6 reaches exit criteria, wherein exit criteria are as follows: when total increase absorption
Between reach preset limit condition or Non-Linear Programming optimization object function value is not improved twice in succession；If so, exiting solution
Process, and using the adsorption time obtained at this time as the optimal adsorption time of the pressure-swing absorption apparatus；Otherwise, it modifies described non-
Adsorption time variable in linear programming model, and return step S6.
Further, the absorbing balance equation in the step S1 are as follows:
Wherein, θiIt indicates in mixed gas to be adsorbed, the coverage rate of gas component i on certain layer of adsorbent；PiIt indicates wait inhale
In attached mixed gas, the partial pressure of gas component i；BiIndicate that Langmuir absorption of the gas component i on this layer of adsorbent is normal
Number；BijIndicate Langmuir absorption of the component i on this layer of adsorbent in the binary gas mixture comprising component i and component j
Constant；KijIndicate that the component j when adsorbing on this layer of adsorbent of the binary gas mixture comprising component i and component j inhales component i
The influence degree of attached effect；Ki,mixIndicate suction-operated of all gas component to gas component i in mixed gas to be adsorbed
Affecting parameters.
Further, the design parameter of the pressure-swing absorption apparatus in the step S2 include pressure-swing absorption apparatus height, it is interior
Diameter and adsorbent inventory, classification, Kong Rong and specific surface area；The operating parameter of pressure-swing absorption apparatus includes raw gas flow, group
At and adsorption operations temperature, pressure and theoretical time of break-through.
Further, the adsorption equilibrium kinetic parameter of the mathematical simulation model of the pressure-swing absorption apparatus in the step S2
It include: diffusion coefficient, mass tranfer coefficient, pelect number and Langmuir adsorption equilibrium costant.
Further, judge whether product hydrogen composition and flow meet default calculate and require to refer to judgement in the step S4
Product hydrogen composition and flow and the product hydrogen of industrial actual device acquisition in step S3 solving result form and flow it is opposite
Whether deviation controls within 1%~5%.
Second aspect, the present invention also provides a kind of optimal adsorption times of pressure-swing absorption apparatus to determine system, comprising:
First modeling unit, for loading the difference of adsorbent classification according to pressure-swing absorption apparatus, by pressure-swing absorption apparatus
It is divided into different adsorption layers, and using absorbing balance equation, mass transfer rate equation and total mass transfer equilibrium equation, establishes the change
Press the mathematical simulation model of adsorbent equipment；
Initial value setup unit, for the design parameter and operating parameter according to the pressure-swing absorption apparatus, described in setting
The adsorption equilibrium kinetic parameter initial value of the mathematical simulation model of pressure-swing absorption apparatus；
First solves unit, carries out Mathematical for the mathematical simulation model to the pressure-swing absorption apparatus, obtains and produce
Product hydrogen composition and flow, while obtaining the time that predetermined component gas in unstripped gas penetrates predetermined adsorption layer；
First judging unit, the product hydrogen composition in solving result for judging the first solution unit are with flow
It is no to meet default calculating requirement, if not meeting pre-designed calculation requirement, correct the adsorption equilibrium in the initial value setup unit
Kinetic parameter initial value；If meeting default calculate to require, the second modeling unit is executed；
Second modeling unit, for establishing the Nonlinear programming Model of the pressure-swing absorption apparatus；
Second solves unit, solves for the Nonlinear programming Model to the pressure-swing absorption apparatus；When solving,
Using the adsorption time of the pressure-swing absorption apparatus as optimized variable, to maximize product hydrogen retrieval rate as target function value, to produce
It is about that product hydrogen hydrogen purity, which cannot penetrate predetermined adsorption layer more than or equal to predetermined component gas in default Reinheitszahl and unstripped gas,
Beam condition；Wherein, the initial value of the adsorption time of the pressure-swing absorption apparatus is configured according to the time of break-through of theoretical calculation；
Second judgment unit, for judging whether the solution in the second solution unit reaches exit criteria, wherein move back
Condition out are as follows: total increase adsorption time reaches preset limit condition or Non-Linear Programming optimization object function value does not have twice in succession
It improves；If so, exiting solution procedure, and using the adsorption time obtained at this time as the optimal absorption of the pressure-swing absorption apparatus
Time；Otherwise, the adsorption time variable in the Nonlinear programming Model is modified, and returns and continues to execute the second solution unit.
Further, the absorbing balance equation in first modeling unit are as follows:
Wherein, θiIt indicates in mixed gas to be adsorbed, the coverage rate of gas component i on certain layer of adsorbent；PiIt indicates wait inhale
In attached mixed gas, the partial pressure of gas component i；BiIndicate that Langmuir absorption of the gas component i on this layer of adsorbent is normal
Number；BijIndicate Langmuir absorption of the component i on this layer of adsorbent in the binary gas mixture comprising component i and component j
Constant；KijIndicate that the component j when adsorbing on this layer of adsorbent of the binary gas mixture comprising component i and component j inhales component i
The influence degree of attached effect；Ki,mixIndicate suction-operated of all gas component to gas component i in mixed gas to be adsorbed
Affecting parameters.
Further, the design parameter of the pressure-swing absorption apparatus in the initial value setup unit includes pressure-swing absorption apparatus
Highly, internal diameter and adsorbent inventory, classification, Kong Rong and specific surface area；The operating parameter of pressure-swing absorption apparatus includes unstripped gas
Flow, composition and adsorption operations temperature, pressure and theoretical time of break-through.
Further, the adsorption equilibrium of the mathematical simulation model of the pressure-swing absorption apparatus in the initial value setup unit is dynamic
Mechanics parameter includes: diffusion coefficient, mass tranfer coefficient, pelect number and Langmuir adsorption equilibrium costant.
Further, first judging unit judges whether product hydrogen composition and flow meet default calculate and require to be to sentence
The product hydrogen that product hydrogen composition and flow and industrial actual device in disconnected first solution unit solving result obtain forms and stream
Whether the relative deviation of amount controls within 1%~5%.
As shown from the above technical solution, the optimal adsorption time of pressure-swing absorption apparatus provided by the invention determines method and is
System is poisoned guaranteeing that the adsorbent in up-to-standard product hydrogen, yield maximization and adsorbent equipment is not polluted by certain components
Etc. under the premise of factors, the comprehensive optimal adsorption time for obtaining pressure-swing absorption apparatus, so as to effectively improve pressure-variable adsorption
The operation of device is horizontal, under the premise of ensuring hydrogen recycling quality, efficiency and not contaminated adsorbent, can effectively extend suction
Improve Business Economic Benefit attached dose of operation cycle.
Detailed description of the invention
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technical description to be briefly described, it should be apparent that, the accompanying drawings in the following description is the present invention
Some embodiments for those of ordinary skill in the art without creative efforts, can also basis
These attached drawings obtain other attached drawings.
Fig. 1 is the flow chart that the optimal adsorption time of pressure-swing absorption apparatus that one embodiment of the invention provides determines method；
Fig. 2 be another embodiment of the present invention provides the optimal adsorption time of pressure-swing absorption apparatus determine the structural representation of system
Figure.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below in conjunction with the embodiment of the present invention
In attached drawing, the technical scheme in the embodiment of the invention is clearly and completely described, it is clear that described embodiment is
A part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art
Every other embodiment obtained without creative efforts, shall fall within the protection scope of the present invention.
One embodiment of the invention provides a kind of optimal adsorption time of pressure-swing absorption apparatus and determines method, shown in Figure 1
Flow chart, this method comprises the following steps:
Step 101: loading the difference of adsorbent classification according to pressure-swing absorption apparatus, pressure-swing absorption apparatus is divided into difference
Adsorption layer establish the pressure-swing absorption apparatus and using absorbing balance equation, mass transfer rate equation and total mass transfer equilibrium equation
Mathematical simulation model.
In this step, the pressure-swing absorption apparatus is referred mainly to reform hydrogen, low point of refinery gas, refinery's refinery dry gas, water
One or more of pressure-swing absorption apparatus for raw material in steam cracking hydrogen manufacturing conversion gas.
In this step, the transformation is established using absorbing balance equation, mass transfer rate equation and total mass transfer equilibrium equation
The mathematical simulation model of adsorbent equipment.It is understood that in this step, using absorbing balance equation, mass transfer rate equation
With total mass transfer equilibrium equation, the mathematical simulation model for establishing the pressure-swing absorption apparatus refers to, using absorbing balance equation, mass transfer
Rate equation and total mass transfer equilibrium equation establish the mathematical simulation model of each adsorption layer in pressure-swing absorption apparatus respectively.Wherein,
The entrance initial value that calculated result of the unstripped gas through a certain adsorption layer is calculated as the simulation of next adsorption layer.
Specifically, it is assumed that pressure and temperature are invariable, and flow model uses axial dispersion plug flow model, by total mass transfer
Equilibrium equation, which calculates, adsorbs caused change in flow, and mass transfer rate equation uses linear driving force model (LDF), adsorption equilibrium side
A kind of improved Langmuir model description of Cheng Caiyong.
In this step, each model equation is as follows:
The mass transfer equilibrium equation of gas component i in element of volume:
Wherein, DLIndicate bed axial diffusion coefficient, m2/s；CiIndicate component i gas phase total concentration, mol/m3；V indicates gas
Flow velocity degree, m/s；ρPIndicate density of gas phase under adsorptive pressure P, kg/m3；ε indicates Molecular Adsorption bed porosity, dimensionless；Table
Show component i adsorption equilibrium concentration, mol/kg.
Total mass transfer equilibrium equation:
Wherein, C indicates bed gas phase concentration, mol/m3；Other parameters meaning is same as above.
Mass transfer rate equation:
Wherein, kiIndicate gas solid transfer coefficient, s；Indicate component i adsorbent bed gas phase concentration, mol/kg；Indicate component
I adsorption equilibrium concentration, mol/kg.
In specific calculate, by adsorption tower bed (pressure-swing absorption apparatus) from tower bottom to tower top, not according to adsorbent classification
With different infinitesimal sections (calculating needs according to practical, same adsorbent layer can also be divided into multiple infinitesimal sections) is divided into, often
The calculated result of one infinitesimal section outlet calculates initial value as next infinitesimal section entrance, successively calculates to absorption tower top, if adsorption tower
It pushes up calculated result and actual value deviation is larger, then return to tower bottom the first infinitesimal section, modification, adjustment relevant parameter.Each infinitesimal section
All using above-mentioned several governing equations modeling, simultaneous solution.Different component is calculated by adsorbent by absorbing balance equation
Adsorbance, the time by the mass transfer rate equation calculation component Jing Guo infinitesimal section, mass transfer material balance equation (total mass transfer material side
The material equation of journey and one-component) mainly pass through a material balance relationship of description component disengaging infinitesimal section, calculating group
Divide the character (concentration, flow etc.) in infinitesimal section exit.
Wherein, absorbing balance equation are as follows:
Wherein, θiIt indicates in mixed gas to be adsorbed, the coverage rate of gas component i on certain layer of adsorbent；PiIt indicates wait inhale
In attached mixed gas, the partial pressure of gas component i, 106Pa；BiIndicate that Langmuir of the gas component i on this layer of adsorbent is inhaled
Attached constant, 106Pa-1；BijIndicate orchid of the component i on this layer of adsorbent in the binary gas mixture comprising component i and component j
Ge Miaoer absorption constant；KijIndicate the component when adsorbing on this layer of adsorbent of the binary gas mixture comprising component i and component j
Influence degree of the j to component i suction-operated；Ki,mixIndicate that all gas component is to gas component i in mixed gas to be adsorbed
Suction-operated affecting parameters.
It should be noted that the absorbing balance equation that the present embodiment uses is based on improved Langmuir model.Below
Improved Langmuir model is introduced:
It is main to be described using one pack system Langmuir model or the Langmuir model of extension in current adsorbing separation field
The Phase Equilibria of adsorption process.But one side one pack system Langmuir model is suitable for studying the absorption of one-component gas
Journey research does not consider influencing each other between different component, cannot describe the adsorption process of multicomponent gaseous mixture；On the other hand it extends
Langmuir model be the wide description multicomponent gas-solid adsorption process of application in recent years model, theoretically need experiment true
Determine the adsorption equilibrium costant of various components on the sorbent in mixed atmosphere to be calculated again, but due to the gas more than two components
The acquisition of adsorption equilibrium costant is extremely difficult, therefore, when the model practical application, generally still uses the one pack system Lange of the component
Miao Er absorption constant replaces the adsorption equilibrium costant of the component in gaseous mixture, and it is flat that such simplified processing must increase gaseous mixture
The inaccuracy that the adsorbance that weighs calculates.For this technical problem, the present embodiment provides a kind of improved Langmuir model, this
The improved Langmuir model of kind being capable of Accurate Determining multi component adsorption process adsorbance.
The establishment process of absorbing balance equation provided in this embodiment is given below:
A, by laboratory facilities or data searching, each gas component is acquired in mixed gas to be determined respectively in same absorption
One pack system Langmuir model on agent S obtains the one pack system Langmuir absorption constant B of each gas componenti；Wherein, described
Mixed gas to be determined includes n kind gas component, 1≤i≤n altogether.
B, according to the gas composition of mixed gas to be determined, the gas of every two kinds of components is configured to binary gas and is mixed
Object is prepared obtain altogetherGroup binary gas mixture；Wherein, the gas of every two kinds of components is being configured to binary gas mixture
When, the molar ratio of two kinds of component gas can be any molar ratio in binary gas mixture, it is preferable that two kinds of gas components
Molar ratio is 1:1.
C, Langmuir absorption of each gas component on the adsorbent in every group of binary gas mixture is obtained respectively
Constant Bij, wherein BijIndicate orchid of the component i on the adsorbent S in the binary gas mixture comprising component i and component j
Ge Miaoer absorption constant；The step can be obtained by experiment.
D, the binary interaction parameter K in every group of binary gas mixture between gas component is obtained respectivelyij, wherein Kij
=Bij/Bi, KijIndicate the binary gas mixture comprising component i and component j when being adsorbed on the adsorbent S component j to group
Divide the influence degree of i suction-operated；Wherein, if 0 < Kij< 1, then it represents that gas component j has the adsorption process of gas component i
There is inhibiting effect；If Kij=1, then it represents that gas component j does not influence or influence on the adsorption process of gas component i minimum；
As i=j, Kij=1；If Kij> 1, then it represents that gas component j has facilitation to the adsorption process of gas component i.Its
In, KijCloser to 1, indicate that components influence is smaller, KijDeviation 1 is bigger, shows that components influence is stronger.
E, according to the binary interaction parameter K between gas component in the binary gas mixture of step d acquisitionij, obtain
Suction-operated parameter K of all gas component to gas component i in mixed gas to be determinedi,mix；In this step, by as follows
Mode obtains in mixed gas to be determined all gas component to the suction-operated parameter K of gas component ii,mix:
Wherein, yjIndicate that gas component j influences regulatory factor, y to the suction-operated of gas component ijExist for gas component j
Shared gas volume fractions in mixed gas to be determined.
F, according to all gas component in mixed gas to be determined to the suction-operated parameter K of gas component ii,mix, establish
The gas-solid adsorption equilibrium equation of mixed gas to be determined:
Wherein, θiIndicate the coverage rate of gas component i on adsorbent in mixed gas to be determined, PiIndicate mixing to be determined
The partial pressure of gas component i in gas, 106Pa, BiIndicate Langmuir absorption constant of the gas component i on the adsorbent,
106Pa-1；.
G, it solves equation and obtains adsorbance of each gas component on adsorbent S.
Step 102: according to the design parameter and operating parameter of the pressure-swing absorption apparatus, setting the pressure-swing absorption apparatus
Mathematical simulation model adsorption equilibrium kinetic parameter initial value.
In this step, the design parameter of pressure-swing absorption apparatus includes pressure-swing absorption apparatus height, internal diameter and adsorbent dress
The amount of filling out, classification, Kong Rong and specific surface area；The operating parameter of pressure-swing absorption apparatus includes raw gas flow, composition and adsorption operations
Temperature, pressure and theoretical time of break-through.The adsorption equilibrium kinetic parameter of the mathematical simulation model of pressure-swing absorption apparatus includes: to expand
Dissipate coefficient, mass tranfer coefficient, pelect number and Langmuir adsorption equilibrium costant.
Step 103: Mathematical is carried out to the mathematical simulation model of the pressure-swing absorption apparatus, obtain product hydrogen composition and
Flow, while obtaining the time that predetermined component gas in unstripped gas penetrates predetermined adsorption layer.
In this step, it when the mathematical simulation model to the pressure-swing absorption apparatus carries out Mathematical, needs to obtain
Predetermined component gas penetrates the time of predetermined adsorption layer in unstripped gas, to mention for the partially restrained condition in subsequent step 106
For foundation.
For example, it is assumed that the design parameter and operating parameter of a certain pressure-swing absorption apparatus (adsorption tower) are as shown in the following table 1 and 2.
Table 3 is unstripped gas, product hydrogen, stripping gas data.So for the adsorption tower, the time of break-through for needing to obtain mainly is related to
And H2O finally penetrates the time of break-through of layer of silica gel, C through alumina bed2+ hydro carbons is finally worn through alumina layer, layer of silica gel
The time of break-through of saturating active carbon layer, CH4Through alumina layer, layer of silica gel, active carbon layer and finally penetrate when penetrating of molecular sieve layer
Between.
Table 1 adsorbs tower section design parameter
2 adsorption tower operating parameter of table
| Project | Content |
| Adsorptive pressure, MPa | 2.1 |
| Material temperature, DEG C | 30~40 |
| Process flow | VPSA, 6-2-3 |
| Single column adsorption time, s | 210 |
3 pressure-swing absorption apparatus stream stock information of table
Step 104: whether product hydrogen composition and flow in 103 solving result of judgment step, which meet default calculate, requires,
If not meeting pre-designed calculation requirement, the adsorption equilibrium kinetic parameter initial value in amendment step 102；If meeting default calculate
It is required that thening follow the steps 105.
In this step, judge whether product hydrogen composition and flow meet default calculate and require to refer to that judgment step 103 is asked
The product hydrogen that product hydrogen composition and flow and industrial actual device in solution result obtain forms and whether the relative deviation of flow
Control is within 1%~5%.
It, can be based on real when the product hydrogen composition in step 103 solving result, which is unsatisfactory for default calculating with flow, to be required
Adsorption equilibrium kinetic parameter in border industry park plan data correcting step 102.
Step 105: establishing the Nonlinear programming Model of the pressure-swing absorption apparatus.
Step 106: the Nonlinear programming Model of the pressure-swing absorption apparatus is solved；When solving, with the change
The adsorption time for pressing adsorbent equipment is optimized variable, pure with product hydrogen hydrogen to maximize product hydrogen retrieval rate as target function value
It is constraint condition that degree, which is greater than or equal to predetermined component gas in default Reinheitszahl and unstripped gas to penetrate predetermined adsorption layer,；Its
In, the initial value of the adsorption time of the pressure-swing absorption apparatus is configured according to the time of break-through of theoretical calculation.
In this step, the product hydrogen retrieval rate is defined as the ratio of pure hydrogen flowrate and the pure hydrogen flowrate in charging in product
Value.In this step, the default Reinheitszahl in preset condition is preferably 99.9%.In this step, in order to guarantee pressure-variable adsorption
For the adsorption layer of device from pollution, predetermined suction cannot be penetrated by also needing to set predetermined component gas in unstripped gas in constraint condition
Attached layer.For example, can arrange: H for the unstripped gas and adsorption tower of above-mentioned example2O does not penetrate silica gel bed, i.e. tAbsorption< tH2O,
C2+ heavy hydrocarbon does not penetrate active carbon bed, i.e. tAbsorption< tC2+, CH4Do not penetrate mol sieve beds, i.e. tAbsorption< tCH4。
Since the solution procedure to Nonlinear programming Model can be realized by dedicated solver, belong to the prior art, therefore
This will not be detailed here.
Step 107: whether the solution of judgment step 106 reaches exit criteria, wherein exit criteria are as follows: total to increase absorption
Time reaches preset limit condition or Non-Linear Programming optimization object function value is not improved twice in succession；It is asked if so, exiting
Solution preocess, and using the adsorption time obtained at this time as the optimal adsorption time of the pressure-swing absorption apparatus；Otherwise, described in modification
Adsorption time variable in Nonlinear programming Model, and return step 106.
In this step, need whether the solution of judgment step 106 reaches exit criteria.Here, exit criteria refers to: total
Increase adsorption time and reaches preset limit condition.For example, preset limit condition is total increase time≤25s.So increase when total
When adsorption time reaches 25s, then meet exit criteria, solution procedure, and the adsorption time that will be obtained at this time can be exited at this time
Optimal adsorption time as the pressure-swing absorption apparatus.In addition, Non-Linear Programming optimization object function value ought not have twice in succession
When having improvement, increases whether adsorption time reaches the preset limit condition regardless of total, equally exit solution procedure.And work as step
When 106 solution is not up to exit criteria, continued by way of adsorption time variable modifying in the Nonlinear programming Model
Carry out optimal solution.For example, increasing 0.5%~5% on the basis of adsorption time initial value or increasing a fixed value, such as increase
5s continues Optimization Solution until meeting exit criteria.
For example, as shown in table 4 using the optimum results that method described in the present embodiment obtains, it can be seen that with current operation work
Condition is compared, and adsorption time increases to 218s by 210s, and hydrogen recovery rate increases to 83.01% by 77.79%, and does not cause H2O
Penetrate layer of silica gel, C2 +Heavy hydrocarbon does not penetrate active carbon layer, CH4Adsorption effect also within Con trolling index.
4 optimum results of table
| Calculated result of the present invention | Former operating condition result | |
| Adsorption time, s | 218 | 210 |
| Hydrogen recovery rate, % | 83.01 | 77.79 |
Method, which is illustrated, to be determined to optimal adsorption time provided by the invention below by another specific example.
Wherein, table 5, table 6 be certain refinery's steam pyrolysis device for producing hydrogen conversion gas concentrate pressure-swing absorption apparatus it is original
Design parameter and operating parameter, table 7 are that pressure-swing absorption apparatus passes in and out material information.Since enterprise's production procedure adjusts, plan will
The pressure-swing absorption apparatus is sent into one hydrogeneous logistics, and table 8 is the stream stock information.
The mathematical simulation model and Nonlinear programming Model of pressure-swing absorption apparatus are established according to step shown in Fig. 1, are set non-
The maximum of adsorption time is total in linear programming model increases the time as 15s.Subsequently into iterative solution process, until meeting condition
It exits.
Finally obtained optimum results are as shown in table 9, it can be seen that compared with current operation operating condition, adsorption time is by 225s
It reduces to 221s, hydrogen recovery rate is down to 88.31% by 88.48%, does not cause H2O penetrates layer of silica gel, C2 +Heavy hydrocarbon does not penetrate work
Property layer of charcoal, CH4Adsorption effect also within Con trolling index.If adsorption time is not reduced, easily make C2 +Heavy hydrocarbon penetrates active carbon
Layer, causes adsorbent of molecular sieve to be poisoned.It is understood that be not that the longer the better for adsorption time compared with current operation operating condition,
But need while considering whether recycling quality, recovery efficiency and the adsorbent of product hydrogen are contaminated, the present invention is examined in synthesis
Under the premise of considering these conditions, optimal adsorption time is obtained.
Table 5 adsorbs tower section design parameter
6 adsorption tower operating parameter of table
| Project | Content |
| Adsorptive pressure, MPa | 2.1 |
| Material temperature, DEG C | 30~40 |
| Process flow | 10-1-6 |
| Single column adsorption time, s | 225 |
7 pressure-swing absorption apparatus stream stock information of table
The hydrogeneous stream stock information of table 8
| Hydrogeneous stream stock | |
| Flow, Nm3/h | 11340 |
| Composition, % | |
| H2 | 75.49 |
| N2 | 0 |
| CH4 | 15.87 |
| C2H6 | 2.98 |
| C3H8 | 2.56 |
| C4H10 | 3.10 |
| H2O | 0 |
| H2S | 30ppm |
| ∑ | 100 |
9 optimum results of table
| Calculated result of the present invention | Former operating condition result | |
| Adsorption time, s | 221 | 225 |
| Hydrogen recovery rate, % | 88.31 | 88.48 |
As shown from the above technical solution, the optimal adsorption time determination side of pressure-swing absorption apparatus provided in an embodiment of the present invention
Method is poisoned guaranteeing that the adsorbent in up-to-standard product hydrogen, yield maximization and adsorbent equipment is not polluted by certain components
Etc. under the premise of factors, the comprehensive optimal adsorption time for obtaining pressure-swing absorption apparatus, so as to effectively improve pressure-variable adsorption
The operation of device is horizontal, under the premise of ensuring hydrogen recycling quality, efficiency and not contaminated adsorbent, can effectively extend suction
Improve Business Economic Benefit attached dose of operation cycle.
Another embodiment of the present invention additionally provides a kind of optimal adsorption time of pressure-swing absorption apparatus and determines system, referring to fig. 2,
The system includes: the first modeling unit 21, initial value setup unit 22, first solution unit 23, the first judging unit 24, second
Modeling unit 25, second solves unit 26 and second judgment unit 27, in which:
First modeling unit 21 fills pressure-variable adsorption for loading the difference of adsorbent classification according to pressure-swing absorption apparatus
It sets and is divided into different adsorption layers, and use absorbing balance equation, mass transfer rate equation and total mass transfer equilibrium equation, described in foundation
The mathematical simulation model of pressure-swing absorption apparatus；
Initial value setup unit 22 sets institute for the design parameter and operating parameter according to the pressure-swing absorption apparatus
State the adsorption equilibrium kinetic parameter initial value of the mathematical simulation model of pressure-swing absorption apparatus；
First solves unit 23, carries out Mathematical for the mathematical simulation model to the pressure-swing absorption apparatus, obtains
Product hydrogen composition and flow, while obtaining the time that predetermined component gas in unstripped gas penetrates predetermined adsorption layer；
First judging unit 24, the product hydrogen composition and flow in solving result for judging the first solution unit
Whether default calculate of satisfaction requires, if not meeting pre-designed calculation requirement, the absorption corrected in the initial value setup unit is flat
Weigh kinetic parameter initial value；If meeting default calculate to require, the second modeling unit is executed；
Second modeling unit 25, for establishing the Nonlinear programming Model of the pressure-swing absorption apparatus；
Second solves unit 26, solves for the Nonlinear programming Model to the pressure-swing absorption apparatus；It is solving
When, using the adsorption time of the pressure-swing absorption apparatus as optimized variable, to maximize product hydrogen retrieval rate as target function value, with
Product hydrogen hydrogen purity cannot penetrate predetermined adsorption layer more than or equal to predetermined component gas in default Reinheitszahl and unstripped gas
Constraint condition；Wherein, the initial value of the adsorption time of the pressure-swing absorption apparatus is set according to the time of break-through of theoretical calculation
It sets；
Second judgment unit 27, for judging whether the solution in the second solution unit reaches exit criteria, wherein
Exit criteria are as follows: total increase adsorption time reaches preset limit condition or Non-Linear Programming optimization object function value does not have twice in succession
There is improvement；If so, exiting solution procedure, and using the adsorption time obtained at this time as the optimal suction of the pressure-swing absorption apparatus
The attached time；Otherwise, the adsorption time variable in the Nonlinear programming Model is modified, and returns and continues to execute the second solution list
Member.
A kind of absorbing balance equation in optional embodiment, in first modeling unit 21 are as follows:
Wherein, θiIt indicates in mixed gas to be adsorbed, the coverage rate of gas component i on certain layer of adsorbent；PiIt indicates wait inhale
In attached mixed gas, the partial pressure of gas component i；BiIndicate that Langmuir absorption of the gas component i on this layer of adsorbent is normal
Number；BijIndicate Langmuir absorption of the component i on this layer of adsorbent in the binary gas mixture comprising component i and component j
Constant；KijIndicate that the component j when adsorbing on this layer of adsorbent of the binary gas mixture comprising component i and component j inhales component i
The influence degree of attached effect；Ki,mixIndicate suction-operated of all gas component to gas component i in mixed gas to be adsorbed
Affecting parameters.
In a kind of optional embodiment, the design parameter packet of the pressure-swing absorption apparatus in the initial value setup unit 22
Include pressure-swing absorption apparatus height, internal diameter and adsorbent inventory, classification, Kong Rong and specific surface area；The operation of pressure-swing absorption apparatus
Parameter includes raw gas flow, composition and adsorption operations temperature, pressure and theoretical time of break-through.
In a kind of optional embodiment, the mathematical simulation mould of the pressure-swing absorption apparatus in the initial value setup unit 22
The adsorption equilibrium kinetic parameter of type includes: diffusion coefficient, mass tranfer coefficient, pelect number and Langmuir adsorption equilibrium costant.
In a kind of optional embodiment, it is pre- that first judging unit 24 judges whether product hydrogen composition and flow meet
Design calculate require be judge first solution 23 solving result of unit in product hydrogen composition and flow with industry actual device acquisition
Product hydrogen composition and the relative deviation of flow whether control within 1%~5%.
The optimal adsorption time of pressure-swing absorption apparatus described in the embodiment of the present invention determines that system can be used for executing above-mentioned reality
It applies the optimal adsorption time of pressure-swing absorption apparatus described in example and determines method, principle is similar with technical effect, and and will not be described here in detail.
In the description of the present invention, relational terms such as first and second and the like be used merely to an entity or
Operation is distinguished with another entity or operation, and without necessarily requiring or implying between these entities or operation, there are any
This actual relationship or sequence.Moreover, the terms "include", "comprise" or its any other variant be intended to it is non-exclusive
Property include so that include a series of elements process, method, article or equipment not only include those elements, but also
Further include other elements that are not explicitly listed, or further include for this process, method, article or equipment it is intrinsic
Element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that including described
There is also other identical elements in the process, method, article or equipment of element.
The above examples are only used to illustrate the technical scheme of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
Invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these are modified or replace
It changes, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (10)
1. a kind of optimal adsorption time of pressure-swing absorption apparatus determines method characterized by comprising
Step S1: the difference of adsorbent classification is loaded according to pressure-swing absorption apparatus, pressure-swing absorption apparatus is divided into different suctions
Attached layer, and using absorbing balance equation, mass transfer rate equation and total mass transfer equilibrium equation, establish the number of the pressure-swing absorption apparatus
Learn simulation model；
Step S2: according to the design parameter and operating parameter of the pressure-swing absorption apparatus, the number of the pressure-swing absorption apparatus is set
Learn the adsorption equilibrium kinetic parameter initial value of simulation model；
Step S3: carrying out Mathematical to the mathematical simulation model of the pressure-swing absorption apparatus, obtain product hydrogen composition and flow,
The time that predetermined component gas in unstripped gas penetrates predetermined adsorption layer is obtained simultaneously；
Step S4: whether product hydrogen composition and flow in judgment step S3 solving result, which meet default calculate, requires, if less than
Default calculate of foot requires, then the adsorption equilibrium kinetic parameter initial value in amendment step S2；If meeting default calculate to require,
Execute step S5；
Step S5: the Nonlinear programming Model of the pressure-swing absorption apparatus is established；
Step S6: the Nonlinear programming Model of the pressure-swing absorption apparatus is solved；When solving, with the pressure-variable adsorption
The adsorption time of device is that optimized variable is greater than using maximizing product hydrogen retrieval rate as target function value with product hydrogen hydrogen purity
Or cannot penetrate predetermined adsorption layer equal to predetermined component gas in default Reinheitszahl and unstripped gas is constraint condition；Wherein, institute
The initial value for stating the adsorption time of pressure-swing absorption apparatus is configured according to the time of break-through of theoretical calculation；
Step S7: whether the solution of judgment step S6 reaches exit criteria, wherein exit criteria are as follows: total adsorption time that increases reaches
Non-Linear Programming optimization object function value is not improved to preset limit condition or twice in succession；If so, solution procedure is exited,
And using the adsorption time obtained at this time as the optimal adsorption time of the pressure-swing absorption apparatus；Otherwise, it modifies described non-linear
Adsorption time variable in plan model, and return step S6.
2. the method according to claim 1, wherein the absorbing balance equation in the step S1 are as follows:
Wherein, θiIt indicates in mixed gas to be adsorbed, the coverage rate of gas component i on certain layer of adsorbent；PiIndicate to be adsorbed
In mixed gas, the partial pressure of gas component i；BiIndicate Langmuir absorption constant of the gas component i on this layer of adsorbent；Bij
Indicate Langmuir absorption constant of the component i on this layer of adsorbent in the binary gas mixture comprising component i and component j；
KijIt indicates that the component j when adsorbing on this layer of adsorbent of the binary gas mixture comprising component i and component j adsorbs component i to make
Influence degree；Ki,mixIndicate that all gas component influences the suction-operated of gas component i in mixed gas to be adsorbed
Parameter.
3. the method according to claim 1, wherein the design parameter of the pressure-swing absorption apparatus in the step S2
Including pressure-swing absorption apparatus height, internal diameter and adsorbent inventory, classification, Kong Rong and specific surface area；The behaviour of pressure-swing absorption apparatus
It include raw gas flow, composition and adsorption operations temperature, pressure and theoretical time of break-through as parameter.
4. the method according to claim 1, wherein the mathematical simulation of the pressure-swing absorption apparatus in the step S2
The adsorption equilibrium kinetic parameter of model includes: that diffusion coefficient, mass tranfer coefficient, pelect number and Langmuir adsorption equilibrium are normal
Number.
5. the method according to claim 1, wherein judging that product hydrogen forms and whether is flow in the step S4
The default calculating requirement of satisfaction refers to the composition of the product hydrogen in judgment step S3 solving result and flow and industrial actual device acquisition
Product hydrogen composition and the relative deviation of flow whether control within 1%~5%.
6. a kind of optimal adsorption time of pressure-swing absorption apparatus determines system characterized by comprising
First modeling unit divides pressure-swing absorption apparatus for loading the difference of adsorbent classification according to pressure-swing absorption apparatus
At different adsorption layers, and using absorbing balance equation, mass transfer rate equation and total mass transfer equilibrium equation, establishes the transformation and inhale
The mathematical simulation model of adsorption device；
Initial value setup unit sets the transformation for the design parameter and operating parameter according to the pressure-swing absorption apparatus
The adsorption equilibrium kinetic parameter initial value of the mathematical simulation model of adsorbent equipment；
First solves unit, carries out Mathematical for the mathematical simulation model to the pressure-swing absorption apparatus, obtains product hydrogen
Composition and flow, while obtaining the time that predetermined component gas in unstripped gas penetrates predetermined adsorption layer；
First judging unit, the product hydrogen in solving result for judging the first solution unit forms and whether flow is full
Default calculate of foot requires, if not meeting pre-designed calculation requirement, corrects the adsorption equilibrium power in the initial value setup unit
Learn initial parameter value；If meeting default calculate to require, the second modeling unit is executed；
Second modeling unit, for establishing the Nonlinear programming Model of the pressure-swing absorption apparatus；
Second solves unit, solves for the Nonlinear programming Model to the pressure-swing absorption apparatus；When solving, with institute
The adsorption time for stating pressure-swing absorption apparatus is optimized variable, to maximize product hydrogen retrieval rate as target function value, with product hydrogen
Hydrogen purity, which is greater than or equal to predetermined component gas in default Reinheitszahl and unstripped gas, cannot penetrate predetermined adsorption layer as constraint item
Part；Wherein, the initial value of the adsorption time of the pressure-swing absorption apparatus is configured according to the time of break-through of theoretical calculation；
Second judgment unit, for judging whether the solution in the second solution unit reaches exit criteria, wherein exit item
Part are as follows: total increase adsorption time reaches preset limit condition or Non-Linear Programming optimization object function value does not change twice in succession
Into；If so, exiting solution procedure, and using the adsorption time obtained at this time as when the optimal absorption of the pressure-swing absorption apparatus
Between；Otherwise, the adsorption time variable in the Nonlinear programming Model is modified, and returns and continues to execute the second solution unit.
7. system according to claim 6, which is characterized in that the absorbing balance equation in first modeling unit are as follows:
Wherein, θiIt indicates in mixed gas to be adsorbed, the coverage rate of gas component i on certain layer of adsorbent；PiIndicate to be adsorbed
In mixed gas, the partial pressure of gas component i；BiIndicate Langmuir absorption constant of the gas component i on this layer of adsorbent；Bij
Indicate Langmuir absorption constant of the component i on this layer of adsorbent in the binary gas mixture comprising component i and component j；
KijIt indicates that the component j when adsorbing on this layer of adsorbent of the binary gas mixture comprising component i and component j adsorbs component i to make
Influence degree；Ki,mixIndicate that all gas component influences the suction-operated of gas component i in mixed gas to be adsorbed
Parameter.
8. system according to claim 6, which is characterized in that pressure-swing absorption apparatus in the initial value setup unit
Design parameter includes pressure-swing absorption apparatus height, internal diameter and adsorbent inventory, classification, Kong Rong and specific surface area；Pressure-variable adsorption
The operating parameter of device includes raw gas flow, composition and adsorption operations temperature, pressure and theoretical time of break-through.
9. system according to claim 6, which is characterized in that pressure-swing absorption apparatus in the initial value setup unit
The adsorption equilibrium kinetic parameter of mathematical simulation model includes: diffusion coefficient, mass tranfer coefficient, pelect number and Langmuir absorption
The equilibrium constant.
10. system according to claim 6, which is characterized in that first judging unit judges product hydrogen composition and stream
Whether amount, which meets default calculate, requires to be judge product hydrogen composition in the first solution unit solving result and flow and industry reality
Whether the relative deviation of product hydrogen composition and flow that border device obtains controls within 1%~5%.
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