CN115232636A - Method and apparatus for determining fischer-tropsch catalyst replacement strategy in a run-time reactor - Google Patents
Method and apparatus for determining fischer-tropsch catalyst replacement strategy in a run-time reactor Download PDFInfo
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- C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
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Abstract
The invention provides a method and a device for determining a Fischer-Tropsch catalyst replacement strategy in a reactor during operation, and belongs to the technical field of Fischer-Tropsch synthesis. The method comprises the following steps: obtaining an initial catalyst replacement interval and an initial catalyst replacement ratio; determining a catalyst proportion corresponding to the operation duration based on a pre-established catalyst proportion distribution model, an initial catalyst replacement interval and an initial catalyst replacement proportion; determining the activity of the catalyst corresponding to the operation duration based on a pre-established catalyst deactivation model; determining the comprehensive activity of the catalyst corresponding to the operation duration based on the catalyst activity, the catalyst proportion, the initial catalyst replacement interval and the initial catalyst replacement proportion; determining loss ratio based on a pre-established loss model and comprehensive activity of the catalyst; and adjusting the catalyst replacement interval and the catalyst replacement ratio according to the loss ratio to determine the replacement interval and the replacement ratio for the Fischer-Tropsch catalyst in the replacement reactor. Thus, a suitable replacement strategy can be obtained.
Description
Technical Field
The invention relates to the technical field of Fischer-Tropsch synthesis, in particular to a method and a device for determining a Fischer-Tropsch catalyst replacement strategy in a reactor during operation.
Background
Based on the characteristics of energy structures of rich coal, lean oil and little gas in China and increasingly severe requirements on the environment-friendly performance of oil products, great significance is brought to the rapid development of the indirect coal liquefaction technology based on Fischer-Tropsch synthesis. Compared with the traditional petroleum refining process, the indirect coal liquefaction product is cleaner, and the product scheme is more flexible. Meanwhile, in the face of the complex situations of the international situation and unstable crude oil price, the development of indirect coal liquefaction has certain economic advantages and is also a strategic reserve.
The Fischer-Tropsch synthesis process realizes the conversion of synthesis gas into hydrocarbons under the action of a solid catalyst. In the production process of the coal indirect liquefaction project, the core Fischer-Tropsch synthesis process needs to maintain excellent and stable production performance, and the catalyst in the Fischer-Tropsch synthesis reactor is easy to inactivate due to factors such as oxidation, carbon deposition, sintering and abrasion in the process of participating in the reaction in the reactor. Therefore, in industrial operation, in order to ensure the stability of the catalytic performance, the catalyst in the reactor must be periodically replaced, i.e., a portion of the old catalyst in the reactor is discharged and a corresponding quantity of fresh, reductively activated catalyst is replenished. In industrial production, the replacement operation needs to be carried out on line, and the requirement cannot have great influence on the production process.
Theoretically, in order to maintain the activity and productivity of the catalyst in the reactor at a high level, the larger the amount of the catalyst to be replaced, the better the shorter the replacement interval. However, such an operation causes a large amount of catalyst to be consumed, resulting in problems of high catalyst consumption, low utilization rate, and high cost.
For example, patent application No. CN201710982743.7 discloses an on-line feeding method of catalyst for slurry bed reactor and a special equipment system thereof, which can realize stable, uniform and accurate quantitative feeding of catalyst into slurry bed reactor. The feeding method comprises the steps of metering before the Fischer-Tropsch catalyst is reduced, activating the catalyst by adopting a slurry bed reduction mode, and conveying the catalyst into a Fischer-Tropsch synthesis reactor by virtue of hydraulic power, and has the advantages of large feeding amount application range and accurate numerical value.
The patent with the application number of CN201510695526.0 discloses a system and a method for replacing a catalyst of a slurry bed reactor. The replacement method adopts a replacement method combining the periodic replacement of the catalyst and the massive replacement of the catalyst. The method provides that the interval of replacing the catalyst regularly is 5 days, the replacing amount is 4.5 tons, and the catalyst which is reduced twice continuously is added into the slurry bed reactor once every month in a large amount to complete the large-amount replacement.
The patent with the application number of CN201810494652.3 discloses an online updating device and method for a catalyst of a Fischer-Tropsch synthesis reactor of a slurry bed. The method adopts a fluidized bed reactor to activate the Fischer-Tropsch catalyst, stores the Fischer-Tropsch catalyst in a storage tank, and transfers the Fischer-Tropsch catalyst to a slurry bed Fischer-Tropsch synthesis reactor at a proper time. The method can carry out catalyst replacement and updating of the Fischer-Tropsch synthesis reactor in a short period and a small proportion after a large amount of catalysts are activated.
The above patents describe methods and apparatus for periodically replacing and replacing the catalyst within the fischer-tropsch reactor. The Fischer-Tropsch synthesis reactor is a slurry bed, and the reduction reactor with a new catalyst source comprises a slurry bed and a fluidized bed. The method provided by the patent can confirm that the on-line replacement of the Fischer-Tropsch catalyst can be realized in the Fischer-Tropsch synthesis production process, and the specific numerical values of the discharge amount and the addition amount can be determined. Among the above schemes, some schemes directly give the substitution intervals and the substitution amounts, and some schemes are not clear. The above scheme does not disclose or teach how the displacement intervals and the displacement amounts are determined and can therefore only be adapted to a specific range of production situations.
Disclosure of Invention
It is an aim of embodiments of the present invention to provide a method and apparatus for determining a fischer-tropsch catalyst replacement strategy within a run-time reactor that addresses one or more of the above technical problems.
To achieve the above object, an embodiment of the present invention provides a method for determining a fischer-tropsch catalyst replacement strategy in a reactor on-the-fly, the fischer-tropsch catalyst replacement strategy comprising replacement intervals and replacement proportions for replacing fischer-tropsch catalyst in the reactor, the method comprising: obtaining an initial catalyst replacement interval and an initial catalyst replacement ratio; determining a catalyst proportion corresponding to the operation duration based on a pre-established catalyst proportion distribution model, the initial catalyst replacement interval and the initial catalyst replacement proportion; determining the activity of the catalyst corresponding to the operation duration based on a pre-established catalyst deactivation model; determining a catalyst integrated activity corresponding to the operation time period based on the catalyst activity, the catalyst ratio, the initial catalyst replacement interval, and the initial catalyst replacement ratio; determining a loss ratio based on a pre-established loss model and the comprehensive activity of the catalyst; and adjusting the catalyst replacement interval and the catalyst replacement ratio according to the loss ratio to determine the replacement interval and the replacement ratio for the Fischer-Tropsch catalyst in the replacement reactor.
Optionally, the adjusting the catalyst replacement interval and the catalyst replacement ratio according to the loss ratio includes: obtaining a catalyst replacement interval limit value and a catalyst replacement ratio limit value; selecting an adjusted catalyst replacement interval from a range of catalyst replacement intervals comprising the catalyst replacement interval limit and the initial catalyst replacement interval; and selecting the adjusted catalyst replacement ratio from a catalyst replacement ratio range composed of the catalyst replacement ratio limit value and the initial catalyst replacement ratio.
Optionally, the catalyst distribution ratio model is established by the following formula:
t；
t-τ h ；k·(1-k) n-i T-T- (i-1). DELTA.t, wherein m 0 And m h Adding the catalyst for the start-up stage, h is the number of the added catalyst for the start-up stage, M is the catalyst inventory, k is the replacement ratio, n is the total number of times of replacement, i is the number of replacement, tau h The time interval for adding the catalyst in the start-up stage, T is the operation duration, T is the time for entering the stable replacement stage, and delta T is the catalyst replacement interval.
Optionally, the catalyst activity comprises one or more of: CO conversion, CO 2 Selective, CH 4 Selectivity and C3+ selectivity.
Optionally, the method further comprises determining the integrated activity of the catalyst corresponding to the operation time period by the following formula:
wherein y represents the overall activity of the catalyst and m represents 0 And m h Adding the catalyst for the start-up stage, wherein p is the total times of adding the catalyst for the start-up stage, h is the number of adding the catalyst for the start-up stage, M is the catalyst inventory, k is the replacement ratio, n is the total times of replacement, i is the replacement number, tau h The time interval for adding the catalyst in the start-up stage, T is the operation duration, T is the time for entering the stable displacement stage, Δ T is the catalyst displacement interval, and g (T) is the catalyst activity.
Optionally, the loss model is established in the following manner:
wherein n is the total number of permutations.
Optionally, the initial catalyst replacement interval and the initial catalyst replacement ratio are determined by the reduction time of a predetermined amount of catalyst, wherein the initial catalyst replacement interval is the reduction time of the predetermined amount of catalyst; and the initial catalyst replacement ratio is a ratio of the predetermined amount of catalyst to the total catalyst.
Accordingly, embodiments of the present invention also provide an apparatus for determining a fischer-tropsch catalyst replacement strategy in a reactor during operation, the fischer-tropsch catalyst replacement strategy comprising replacement intervals and replacement proportions for replacing fischer-tropsch catalyst in the reactor, the apparatus comprising: the acquisition module is used for acquiring an initial catalyst replacement interval and an initial catalyst replacement proportion; a determination module to perform the following operations: determining a catalyst proportion corresponding to the operation duration based on a pre-established catalyst proportion distribution model, the initial catalyst replacement interval and the initial catalyst replacement proportion; determining the activity of the catalyst corresponding to the operation duration based on a pre-established catalyst deactivation model; determining a catalyst integrated activity corresponding to the operation time period based on the catalyst activity, the catalyst ratio, the initial catalyst replacement interval, and the initial catalyst replacement ratio; determining loss ratio based on a pre-established loss model and the comprehensive activity of the catalyst; and the adjusting module is used for adjusting the catalyst replacement interval and the catalyst replacement proportion according to the loss ratio so as to determine the replacement interval and the replacement proportion for the Fischer-Tropsch catalyst in the replacement reactor.
In another aspect, the present invention provides a machine-readable storage medium having stored thereon instructions for causing a machine to perform a method for determining a fischer-tropsch catalyst replacement strategy in a reactor at runtime as described in any one of the above.
In another aspect, the invention provides a processor for executing a program which when executed is operable to perform a method for determining a fischer-tropsch catalyst replacement strategy in a run-time reactor as set out in any one of the preceding claims.
Through the technical scheme, the user can adjust the catalyst replacement proportion and the catalyst replacement interval to the values which are most consistent with the user expectation according to the actual requirement. In addition, the technical scheme can also solve the problem of how to quantitatively confirm the catalyst replacement interval and the catalyst replacement ratio based on data, and effectively improves the scientificity and the high efficiency of production decision.
Additional features and advantages of embodiments of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the embodiments of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the embodiments of the invention without limiting the embodiments of the invention. In the drawings:
FIG. 1 is a schematic diagram of a catalyst displacement flow in a Fischer-Tropsch synthesis reaction process according to an embodiment of the present invention;
FIG. 2 is a schematic flow diagram of a method for determining a Fischer-Tropsch catalyst replacement strategy in a reactor on-the-fly in accordance with an embodiment of the present invention;
FIG. 3 is a schematic flow diagram of a method for determining a Fischer-Tropsch catalyst replacement strategy in a reactor on-the-fly in accordance with an embodiment of the present invention;
FIG. 4 is a block diagram of an apparatus for determining a Fischer-Tropsch catalyst replacement strategy in a reactor on-the-fly according to an embodiment of the present invention.
Description of the reference numerals
1. Catalyst reduction activation reactor 2 Fischer-Tropsch synthesis reactor
3. New reduction activation catalyst for slag wax collecting tank 4
5. Old catalyst 6 fresh synthesis gas
7. Oil and tail gas 410 acquisition module
420. Determining module 430 adjustment module
Detailed Description
The following describes in detail embodiments of the present invention with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating embodiments of the invention, are given by way of illustration and explanation only, not limitation.
To facilitate an understanding of the Fischer-Tropsch synthesis reactor catalyst replacement process, it will now be explained with reference to the schematic Fischer-Tropsch synthesis reactor catalyst replacement flow diagram shown in FIG. 1.
As shown in figure 1, a catalyst is placed in the catalyst reduction activation reactor 1, wherein a new reduction activation catalyst 4 and a fresh synthesis gas 6 are sent to the Fischer-Tropsch synthesis reactor 2 to participate in Fischer-Tropsch synthesis reaction, oil products and tail gas 7 generated after the reaction are discharged from the Fischer-Tropsch synthesis reactor 2 and collected, and meanwhile, an old catalyst 5 is also discharged from the Fischer-Tropsch synthesis reactor 2 to the wax residue collection tank 3 and collected. The scheme finishes the replacement of the catalyst by discharging the old catalyst and injecting the new reduction activation catalyst, so that the production process can be maintained in a stable production state.
Based on the catalyst replacement process of the fischer-tropsch synthesis reactor provided by the above embodiment, the invention provides a method for determining a fischer-tropsch catalyst replacement strategy in a reactor during operation, which can help a worker determine an appropriate catalyst replacement interval and a catalyst replacement ratio to achieve the following optimization effects: the practicability of catalyst replacement and the production efficiency are improved while the production stability is ensured. Among them, in the stable production process, it is necessary to keep the catalyst inventory in the reactor in a substantially stable state, and therefore for convenience of description, it is proposed in the present application to describe the substitution amount information of the catalyst by the substitution ratio.
FIG. 2 is a schematic flow diagram of a method for determining a Fischer-Tropsch catalyst replacement strategy in a reactor on-the-fly according to an embodiment of the invention. As shown in FIG. 2, the method for determining an in-reactor Fischer-Tropsch catalyst replacement strategy on the fly includes steps S1210 through S260.
In step S210, an initial catalyst replacement interval and an initial catalyst replacement ratio are acquired.
The obtained initial catalyst replacement interval and initial catalyst replacement ratio may be determined in a manner selected from the following manners: selecting an initial catalyst replacement interval and an initial catalyst replacement ratio from historical production parameters, selecting an initial catalyst replacement interval and an initial catalyst replacement ratio based on accumulated production experience or worker experience, or selecting an initial catalyst replacement interval and an initial catalyst replacement ratio from parameters of a relevant simulated Fischer-Tropsch synthesis reaction, and the like.
Wherein, in order to be able to analyze an accurate and reliable operation time length, it is preferable to take the time length consumed for reducing a batch of catalyst as the initial replacement interval.
For example, the initial catalyst replacement interval is the reduction time of a predetermined amount of catalyst and the initial catalyst replacement ratio is the ratio of the predetermined amount of catalyst to the total catalyst.
Wherein the maximum value of the predetermined amount of the catalyst is based on the maximum reduction amount of the catalyst reduction activation reactor.
Wherein the initial catalyst replacement interval may further consider that the process time is additionally considered on the basis of the reduction time of the predetermined amount of catalyst so as to have a sufficient catalyst replacement preparation time.
In step S220, a catalyst ratio corresponding to the operation time period is determined based on the catalyst ratio distribution model, the initial catalyst replacement interval, and the initial catalyst replacement ratio that are established in advance.
The pre-established catalyst proportion distribution model is mainly used for determining the proportion distribution condition of the catalyst in the Fischer-Tropsch synthesis reactor when the Fischer-Tropsch synthesis reaction is operated to different operation periods.
Considering that a fischer-tropsch synthesis reactor in industrial production runs for a long period and can be divided into a start-up stage and a stable operation stage, the embodiment of the invention also provides a method for establishing a catalyst distribution proportion model aiming at the catalyst replacement characteristics of the two working stages.
In the start-up stage, certain quality of catalyst needs to be transferred into the Fischer-Tropsch synthesis reactor in batches according to the activation capacity of the catalyst reduction activation reactor until the catalyst inventory meets the requirement. In the process, a certain amount of catalyst replacement can be carried out according to the operation conditions, but the replacement ratio and the replacement interval are unstable, and the start-up period is usually less than 500h.
Therefore, a catalyst distribution ratio model at the start-up stage is established by the following formula:
the operation time is t;
the running time is t-tau h . Wherein m is 0 And m h Adding the mass of the catalyst for the start-up stage, h is the number of the added agent for the start-up stage, M is the catalyst inventory, k is the replacement ratio, n is the total replacement times, and tau h The time interval for adding the catalyst in the start-up stage, and t is the running time length.
Wherein the value of h is 1,2,3, … …, p. Corresponding to, m 1 To m p Denotes the mass of catalyst, τ, added in different batches during the start-up phase 1 To tau p Indicating the time intervals between the different batches of catalyst addition during the start-up phase.
The steady metathesis stage is entered after the catalyst inventory is met and the system is stabilized. In the stable operation stage, the Fischer-Tropsch synthesis reactor needs to discharge a certain proportion of used catalyst periodically and supplement new catalyst with the same quality, so that stable production efficiency is achieved while the catalyst inventory is ensured to be stable.
Therefore, the catalyst distribution ratio model for the steady operation stage is established by the following formula: k (1-k) n-i The running time is T-T- (i-1). Delta T. Wherein k is the replacement proportion, n is the total replacement times, i is the replacement serial number, T is the operation duration, T is the time for entering the stable replacement stage, Δ T is the catalyst replacement interval, and the value of i is 1,2,3, … …, n.
Wherein, in advanceWhen the pre-established catalyst distribution proportion model is used initially, the replacement proportion k and the catalyst replacement interval delta t in the model are respectively the obtained initial catalyst replacement proportion k 0 And initial catalyst replacement interval Δ t 0 。
In addition, on the basis of the operating time length, the time to enter the stable metathesis stage and the catalyst metathesis interval, the total number of metathesis times n can be determined based on the following formula:
in step S230, the catalyst activity corresponding to the operation period is determined based on the catalyst deactivation model established in advance.
Depending on the type of catalyst employed in the fischer-tropsch synthesis process, the catalyst activities involved may include one or more of the following: CO conversion, CO 2 Selective, CH 4 Selectivity and C3+ selectivity.
The catalyst deactivation model involved in this step may be a general model based on data or a theoretical model based on mechanism, as long as the catalyst activity according to time can be determined based on the catalyst deactivation model.
For example, a general model based on data may be selected as the catalyst deactivation model. The data can be obtained by a catalyst non-replacement long-period evaluation test of a corresponding small-scale device, the dependent variable of the model is the relative activity of the catalyst (namely the ratio of the activity of the catalyst to the initial activity of the catalyst at a certain moment), and the independent variable of the model is the natural logarithm of time. Wherein the long period of non-replacement by the catalyst should be longer than 1000h, preferably longer than 2000h.
Now, explanation is made by a method of establishing a catalyst deactivation model according to pilot plant experimental data. The time length of the catalyst of the pilot plant experimental batch without replacement for the long period was 2000h. In the method, the fitted catalyst deactivation model is a 6-segment Gaussian mixture model, and the goodness of fit R of the model is verified through multiple times of experimental data 2 Are all more than 97 percent.
Specifically, it is composed of 6 segmentsThe catalyst deactivation model constructed by the Gaussian mixture model is as follows:
where f (x) represents catalyst activity, a, b and c are parameters (depending on pilot plant experimental data), e is the natural logarithm, and x is time dependent (e.g., x is lnt, and t is run length).
In step S240, a catalyst integrated activity corresponding to the operation time period is determined based on the catalyst activity, the catalyst ratio, the initial catalyst replacement interval, and the initial catalyst replacement ratio.
The embodiment of the present invention provides a method for determining the comprehensive activity of the catalyst corresponding to the operation duration by combining the pre-established catalyst proportion distribution model and the pre-established catalyst deactivation model provided in the above embodiments of the present invention, and the comprehensive activity of the catalyst can be specifically determined by the following formula:
wherein y represents the overall activity of the catalyst and m represents 0 And m h The mass of the catalyst added in the start-up stage, p is the total times of adding the catalyst in the start-up stage, h is the number of adding the catalyst in the start-up stage, M is the inventory of the catalyst, k is the displacement ratio, n is the total times of displacement, i is the displacement number, tau h The time interval for adding the catalyst in the start-up stage, T is the operation duration, T is the time for entering the stable displacement stage, Δ T is the catalyst displacement interval, and g (T) is the catalyst activity.
Wherein the substitution ratio k and the catalyst substitution interval Δ t in the formula for determining the integrated activity of the catalyst corresponding to the catalyst distribution ratio model are the same as the substitution ratio k and the catalyst substitution interval Δ t in the catalyst distribution ratio model. For example, in the preliminary use, the replacement ratio k and the catalyst replacement interval Δ t in the formula for determining the comprehensive activity of the catalyst are the initial catalyst replacement ratio k obtained 0 And initial catalyst replacement interval Δ t 0 。
Wherein y ∈ (XCO, YCO) for the overall activity y of the catalyst 2 ,YCH 4 YC3+, etc.), X represents the conversion and Y represents the selectivity.
When the catalyst deactivation model f (x) constructed by the 6-segment gaussian mixture model provided in the above embodiment in step S130 is selected, g (t) = f (lnt) · initial activity value.
The comprehensive activity of the catalyst related in the embodiment of the invention can show the comprehensive activity of the catalyst at different running time points under different catalyst replacement conditions.
In step S250, a loss ratio is determined based on a loss model established in advance and the catalyst integrated activity.
The attrition ratio is used primarily to characterize the effect of the metathesis catalyst on production. On the basis, the embodiment of the invention provides a method for establishing a loss model, so as to be used for loss ratios corresponding to the catalyst replacement intervals and the catalyst replacement ratios.
For industrial production, performance indexes such as oil production, oil-gas consumption per ton and oil-oil consumption per ton are involved, so that the performance indexes at different moments can be cumulatively calculated to obtain total oil production, total gas consumption, total agent consumption and the like. Based on the calculation results, a relationship can be established that comprehensively considers the total oil production, gas consumption, agent consumption and replacement operation cost within the operating time length range.
Specifically, a loss model may be established to determine loss fraction by the following equation:
wherein n is the total number of permutations.
The loss model established based on the method provided by the embodiment of the invention can determine the loss cost in the production process based on the current market, thereby providing an effective and reasonable adjustment direction for the subsequent catalyst replacement proportion and catalyst replacement interval.
In step S260, the catalyst replacement interval and the catalyst replacement ratio are adjusted according to the loss ratio to determine the replacement interval and the replacement ratio for the Fischer-Tropsch catalyst in the replacement reactor.
For adjusting the catalyst replacement interval and the catalyst replacement ratio, an appropriate adjustment mode and an adjustment trend can be selected on the basis of the actual production plan.
For example, the catalyst replacement interval limit and the catalyst replacement ratio limit may be set, and then the adjusted catalyst replacement interval may be selected from the range of catalyst replacement intervals consisting of the catalyst replacement interval limit and the initial catalyst replacement interval, and/or the adjusted catalyst replacement ratio may be selected from the range of catalyst replacement ratios consisting of the catalyst replacement ratio limit and the initial catalyst replacement ratio.
Wherein the catalyst replacement interval limit is dependent upon the elapsed catalyst reduction process throughput and the catalyst replacement ratio limit is dependent upon the catalyst inventory and the catalyst reduction process throughput.
On the basis of determining the catalyst replacement interval limit and the catalyst replacement ratio limit, the catalyst replacement interval and the catalyst replacement ratio may be adjusted in a certain direction and within a restricted range, and the above steps S210 to S250 may be repeated.
After repeating steps S210 to S250 for a plurality of times, a plurality of sets of displacement parameters can be obtained, including the catalyst displacement interval, the catalyst displacement ratio, and the loss ratio corresponding thereto. Therefore, reasonable value-taking basis can be provided for the selection of the catalyst replacement interval and the catalyst replacement proportion in the Fischer-Tropsch synthesis reaction.
For example, the catalyst replacement interval and the catalyst replacement ratio corresponding to the lowest loss ratio value may be optimally selected, or a plurality of sets of catalyst replacement intervals and catalyst replacement ratios may be used as candidate parameters. Specifically, the catalyst replacement interval with the loss ratio within a certain range and the corresponding catalyst replacement ratio can be used as alternative parameters, so that when different production capacities and production requirements are met, a proper catalyst replacement interval and a proper catalyst replacement ratio can be selected and used as a replacement strategy of the fischer-tropsch catalyst in the reactor during operation to replace the fischer-tropsch catalyst in the reactor during operation.
Based on the method for determining the Fischer-Tropsch catalyst replacement strategy in the reactor during operation, provided by the embodiment of the invention, a user can adjust the catalyst replacement ratio and the catalyst replacement interval to values which are most accordant with the user expectation according to actual requirements. The method can solve the problem of how to quantitatively determine the catalyst replacement interval and the catalyst replacement ratio based on data in the industrial production process, and effectively improves the scientificity and the high efficiency of production decision.
The method for determining the Fischer-Tropsch catalyst replacement strategy in the reactor during operation, provided by the embodiment of the invention, provides operability for adjusting the catalyst deactivation model parameters according to the model number of the catalyst for a user, and can also assist the user to obtain a proper catalyst replacement interval and a proper catalyst replacement proportion according to a dynamic market state, so that the scheme is strong in practicability and can be adaptive to the market state.
Embodiments of the present invention further provide a method for determining a fischer-tropsch catalyst replacement strategy in a reactor during operation, and a specific process is shown in fig. 3.
In step S301, the following values are determined: catalyst replacement interval Δ t 0 Catalyst replacement ratio k 0 And an operating time length t, and the number of the primary cycles is recorded as j =0, r =0.
In step S302, the number of replacements is calculated, the catalyst proportion distribution corresponding to each hour within the operation time period t is calculated based on the catalyst proportion distribution models for different operation time periods, and the catalyst activity corresponding to each hour is determined based on the catalyst deactivation model.
In step S303, the comprehensive activity of the catalyst for each hour is determined based on the proportional distribution of the catalyst and the activity of the catalyst corresponding to each hour, and the output value and the loss value corresponding to each hour are calculated at the same time.
In step S304, the total output value and the loss value within the operation time period t are determined based on the performance index, and the total loss ratio is determined.
In step S305Based on the total loss ratio P jr And the corresponding catalyst replacement ratio k j And catalyst replacement interval Δ t r 。
At step S306, j = j +1,k j ＝k 0 +1。
In step S307, it is judged that k j Whether or not greater than
If yes, go to step S308, otherwise go to step S302.
At step S380, r = r +1, Δ t r ＝Δt 0 +1。
In step S309, Δ t is judged r Whether or not it is greater than the upper limit value Δ t Upper limit of If yes, step S310 is executed, otherwise step S302 is executed.
In step S310, the smallest P is confirmed jr And returns the corresponding Δ t r And k j 。
Shown in the current step S310 is a set of permutation intervals and permutation ratios, which correspond to the minimum loss to fraction.
On the basis, the step S310 may be further modified to output and store all of one or more sets of replacement intervals and replacement ratios with loss occupation ratios within a preset range.
The scheme provided by the embodiment of the invention can solve the problem of how to determine the replacement interval and the replacement ratio of the catalyst in industrial production so as to improve the scientificity and the high efficiency of production decision.
The scheme provided by the embodiment of the invention is explained in detail in the stable replacement stage of a certain industrial application Fischer-Tropsch catalyst in an industrial scale slurry bed reactor.
Step 1: determination of initial values of catalyst Displacement intervals and ratios Deltat 0 Is 72h, k 0 At 5%, the operating time t was considered to be 5000h.
And 2, step: the proportional distribution of the catalyst in the reactor was calculated for different residence times.
The method specifically comprises the following steps: (1) confirming the additive condition in the start-up stage; (2) confirming the start of stable replacement time; (3) calculating the total times of replacement; (4) the catalyst ratios were calculated for different retention periods.
And step 3: and establishing a catalyst deactivation model, and calculating the catalyst activity corresponding to different retention time lengths.
The method specifically comprises the following steps: (1) establishing a catalyst deactivation model according to the pilot test experimental data, wherein the pilot test experimental evaluation time is 2000h, the fitted catalyst deactivation model is a 6-section Gaussian mixture model, and the fitting goodness R is 2 Are all more than 97 percent; (2) the initial value of the activity of the catalyst under given industrial conditions; (3) the catalyst activity was calculated for different retention periods.
And 4, step 4: and calculating the comprehensive performance of the catalyst in the reactor at different moments within 5000h of the operation time.
And 5: and calculating the industrial performance indexes of the catalyst at different moments within 5000h of the operation time.
The method specifically comprises the following steps: (1) giving fresh synthesis gas air inflow, effective gas proportion, H2/CO and other parameters, and (2) calculating oil production, ton oil-gas consumption, ton oil-agent consumption and other performance indexes.
And 6: and performing cumulative calculation on the performance indexes at different moments in the operation duration to obtain total oil production, total gas consumption, total agent consumption and the like, establishing a loss model comprehensively considering the total oil production, the total gas consumption, the total agent consumption and the replacement operation cost in the operation duration range, and calculating the loss ratio.
The method specifically comprises the following steps: (1) performing cumulative calculation on the performance indexes at different moments to obtain total oil production, total gas consumption, total agent consumption and the like; (2) obtaining oil product selling price, synthesis gas cost, catalyst cost, reduction operation cost, catalyst replacement cost and other production costs; (3) and calculating the loss ratio.
And 7: and (5) increasing the numerical value of the replacement interval and the replacement proportion, repeating the steps 2 to 6, and obtaining the conditions of different conditions until the constraint limit value is reached.
The method specifically comprises the following steps: (1) confirming the limit value of the constraint condition, wherein the replacement proportion is less than or equal to 11 percent, and the upper limit of the replacement interval is 144h; (2) the loss fraction for different permutation conditions was calculated.
And 8: based on the loss ratio, the optimal replacement interval is determined to be 84h, and the optimal replacement ratio is 11%.
Based on the above specific embodiments, the simulation situation of the performance index, the original industrial actual situation, and the optimized industrial actual situation under the conditions of the optimal replacement interval and the optimal replacement proportion are shown in table 1.
As can be seen from the comparison of table 1, the simulated value obtained by the method of the present invention is very close to the actual value of the industry under the same conditions, and the adjusted optimal replacement interval and optimal replacement ratio obtained by the method of the present invention are highly reliable, and the results of stable operation of the industry under the optimal replacement conditions are lower in gas and oil consumption per ton, higher in oil and solvent consumption per ton, and better in production efficiency, compared with the original industrial results.
FIG. 4 is a block diagram of an apparatus for determining a Fischer-Tropsch catalyst replacement strategy in a reactor on-the-fly according to an embodiment of the present invention. As shown in FIG. 4, the apparatus for determining an in-reactor Fischer-Tropsch catalyst replacement strategy on-the-fly includes an acquisition module 410, a determination module 420, and an adjustment module 430. The obtaining module 410 is configured to obtain an initial catalyst replacement interval and an initial catalyst replacement ratio; the determining module 420 is configured to determine a catalyst proportion corresponding to the operation duration based on a pre-established catalyst proportion distribution model, the initial catalyst replacement interval, and the initial catalyst replacement proportion, determine a catalyst activity corresponding to the operation duration based on a pre-established catalyst deactivation model, determine a catalyst comprehensive activity corresponding to the operation duration based on the catalyst activity, the catalyst proportion, the initial catalyst replacement interval, and the initial catalyst replacement proportion, and determine a loss fraction based on a pre-established loss model and the catalyst comprehensive activity; the adjusting module 430 is configured to adjust the catalyst replacement interval and the catalyst replacement ratio according to the loss proportion to determine a replacement interval and a replacement ratio for adjusting the fischer-tropsch catalyst, and use the replacement interval and the replacement ratio for adjusting the fischer-tropsch catalyst as a replacement strategy for the fischer-tropsch catalyst in the reactor during operation.
The obtaining module is used for obtaining an initial catalyst replacement interval and an initial catalyst replacement proportion, and can also obtain parameter values, coefficients and the like for constructing a model. For example, the obtaining module can also obtain the selling price of oil products, the cost price of the synthesis gas, the cost price of the catalyst, the operation cost price of each replacement, the air inflow of the fresh synthesis gas, the effective gas proportion and the fresh synthesis gas H 2 The initial value of the activity of the catalyst in industrial operation and/or the inactivation model parameters and the like.
Based on various pre-established models, the determining module can determine various data in the operation duration during the corresponding operation, for example, the comprehensive activity of the hybrid catalyst at different times can be determined based on the catalyst proportion distribution conditions of different operation durations and the corresponding catalyst activity based on the catalyst deactivation model, and then the comprehensive activity of the catalyst is used to determine the production performance indexes, such as oil production, ton oil-gas consumption, ton oil-agent consumption and the like, of each time point in each time period. Then, an accumulated value is calculated based on the production performance index of each time point in the operation time length, so that the loss ratio can be determined based on the loss model.
In the process of adjusting the catalyst replacement interval and the catalyst replacement ratio by the adjustment module, the catalyst replacement interval and the catalyst replacement ratio also need to be controlled within the constraint range.
In addition, based on the user requirement, the adjusting module can return the optimal group of data, or can return all group of data meeting the conditions, so that the user can conveniently take the data.
For specific details and benefits of the apparatus for determining a fischer-tropsch catalyst replacement strategy in a runtime reactor provided in accordance with the above-described embodiments of the present invention, reference may be made to the specific details and benefits of the method for determining a fischer-tropsch catalyst replacement strategy in a runtime reactor provided in accordance with the present invention, which will not be described in detail herein.
The device for determining the Fischer-Tropsch catalyst replacement strategy in the reactor during operation comprises a processor and a memory, wherein the acquisition module, the determination module, the adjustment module and the like are stored in the memory as program units, and the processor executes the program units stored in the memory to realize corresponding functions.
The processor comprises a kernel, and the kernel calls the corresponding program unit from the memory. One or more than one inner core can be set, and the proper replacement interval and replacement proportion of the Fischer-Tropsch catalyst can be obtained according to the loss ratio by adjusting the parameters of the inner core.
The memory may include volatile memory in a computer readable medium, random Access Memory (RAM) and/or nonvolatile memory such as Read Only Memory (ROM) or flash memory (flash RAM), and the memory includes at least one memory chip.
Embodiments of the present invention provide a storage medium having stored thereon a program which, when executed by a processor, implements the method for determining a fischer-tropsch catalyst replacement strategy in a reactor at runtime.
Embodiments of the invention provide a processor for running a program, wherein the program is run to perform the method for determining a fischer-tropsch catalyst replacement strategy in a reactor at runtime.
An embodiment of the invention provides an apparatus comprising a processor, a memory, and a program stored on the memory and executable on the processor, the processor implementing the steps of the method for determining a fischer-tropsch catalyst replacement strategy in a reactor at runtime when executing the program. The device herein may be a server, a PC, a PAD, a mobile phone, etc.
There is also provided a computer program product adapted to perform a program, when executed on data processing apparatus, of initializing method steps for determining a fischer-tropsch catalyst replacement strategy in a reactor on-the-fly as provided by any of the embodiments of the invention.
As will be appreciated by one skilled in the art, embodiments of the present application may be provided as a method, system, or computer program product. Accordingly, the present application may take the form of an entirely hardware embodiment, an entirely software embodiment or an embodiment combining software and hardware aspects. Furthermore, the present application may take the form of a computer program product embodied on one or more computer-usable storage media (including, but not limited to, disk storage, CD-ROM, optical storage, and the like) having computer-usable program code embodied therein.
The present application is described with reference to flowchart illustrations and/or block diagrams of methods, apparatus (systems), and computer program products according to embodiments of the application. It will be understood that each flow and/or block of the flow diagrams and/or block diagrams, and combinations of flows and/or blocks in the flow diagrams and/or block diagrams, can be implemented by computer program instructions. These computer program instructions may be provided to a processor of a general purpose computer, special purpose computer, embedded processor, or other programmable data processing apparatus to produce a machine, such that the instructions, which execute via the processor of the computer or other programmable data processing apparatus, create means for implementing the functions specified in the flowchart flow or flows and/or block diagram block or blocks.
These computer program instructions may also be stored in a computer-readable memory that can direct a computer or other programmable data processing apparatus to function in a particular manner, such that the instructions stored in the computer-readable memory produce an article of manufacture including instruction means which implement the function specified in the flowchart flow or flows and/or block diagram block or blocks.
These computer program instructions may also be loaded onto a computer or other programmable data processing apparatus to cause a series of operational steps to be performed on the computer or other programmable apparatus to produce a computer implemented process such that the instructions which execute on the computer or other programmable apparatus provide steps for implementing the functions specified in the flowchart flow or flows and/or block diagram block or blocks.
In a typical configuration, a computing device includes one or more processors (CPUs), input/output interfaces, network interfaces, and memory.
The memory may include forms of volatile memory in a computer readable medium, random Access Memory (RAM) and/or non-volatile memory, such as Read Only Memory (ROM) or flash memory (flash RAM). The memory is an example of a computer-readable medium.
Computer-readable media, including both non-transitory and non-transitory, removable and non-removable media, may implement information storage by any method or technology. The information may be computer readable instructions, data structures, modules of a program, or other data. Examples of computer storage media include, but are not limited to, phase change memory (PRAM), static Random Access Memory (SRAM), dynamic Random Access Memory (DRAM), other types of Random Access Memory (RAM), read Only Memory (ROM), electrically Erasable Programmable Read Only Memory (EEPROM), flash memory or other memory technology, compact disc read only memory (CD-ROM), digital Versatile Discs (DVD) or other optical storage, magnetic cassettes, magnetic tape magnetic disk storage or other magnetic storage devices, or any other non-transmission medium that can be used to store information that can be accessed by a computing device. As defined herein, a computer readable medium does not include a transitory computer readable medium such as a modulated data signal and a carrier wave.
It should also be noted that 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 a … …" does not exclude the presence of another identical element in a process, method, article, or apparatus that comprises the element.
The above are merely examples of the present application and are not intended to limit the present application. Various modifications and changes may occur to those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present application should be included in the scope of the claims of the present application.
Claims (10)
1. A method for determining a fischer-tropsch catalyst replacement strategy for use in a run-time reactor, wherein the fischer-tropsch catalyst replacement strategy comprises replacement intervals and replacement ratios for replacing a fischer-tropsch catalyst in the reactor, the method comprising:
obtaining an initial catalyst replacement interval and an initial catalyst replacement ratio;
determining a catalyst proportion corresponding to the operation duration based on a pre-established catalyst proportion distribution model, the initial catalyst replacement interval and the initial catalyst replacement proportion;
determining the activity of the catalyst corresponding to the operation duration based on a pre-established catalyst deactivation model;
determining a catalyst integrated activity corresponding to the operation time period based on the catalyst activity, the catalyst ratio, the initial catalyst replacement interval, and the initial catalyst replacement ratio;
determining a loss ratio based on a pre-established loss model and the comprehensive activity of the catalyst; and
and adjusting the catalyst replacement interval and the catalyst replacement ratio according to the loss ratio to determine the replacement interval and the replacement ratio for the Fischer-Tropsch catalyst in the replacement reactor.
2. The method of claim 1, wherein said adjusting a catalyst replacement interval and a catalyst replacement ratio based on said attrition ratio comprises:
acquiring a catalyst replacement interval limit value and a catalyst replacement ratio limit value;
selecting an adjusted catalyst replacement interval from a range of catalyst replacement intervals comprising the catalyst replacement interval limit and the initial catalyst replacement interval; and
the adjusted catalyst replacement ratio is selected from a catalyst replacement ratio range consisting of the catalyst replacement ratio limit value and the initial catalyst replacement ratio.
3. The method of claim 1, wherein the catalyst distribution ratio model is established by the following equation:
k·(1-k) n-i ，t-T-(i-1)·Δt，
wherein m is 0 And m h Adding the catalyst for the start-up stage, h is the number of the added catalyst for the start-up stage, M is the catalyst inventory, k is the replacement ratio, n is the total number of times of replacement, i is the number of replacement, tau h The time interval for adding the catalyst in the start-up stage, T is the operation duration, T is the time for entering the stable replacement stage, and delta T is the catalyst replacement interval.
4. The method of claim 1, wherein the catalyst activity comprises one or more of: CO conversion, CO 2 Selective, CH 4 Selectivity and C3+ selectivity.
5. The method of claim 1, further comprising determining the integrated activity of the catalyst corresponding to the length of operation by the following equation:
wherein y represents the overall activity of the catalyst and m represents 0 And m h Adding the mass of the catalyst for the start-up stage, wherein p is the total times of adding the catalyst for the start-up stage, h is the number of adding the catalyst for the start-up stage, M is the catalyst inventory, k is the replacement ratio, nFor the total number of permutations, i is the permutation number, τ h The time interval for adding the catalyst in the start-up stage, T is the operation duration, T is the time for entering the stable displacement stage, Δ T is the catalyst displacement interval, and g (T) is the catalyst activity.
6. The method of claim 1, wherein the loss model is established by:
wherein n is the total number of permutations.
7. The method of claim 1, wherein the initial catalyst replacement interval and the initial catalyst replacement ratio are determined by a reduction time of a predetermined amount of catalyst,
wherein the initial catalyst replacement interval is the reduction time of the predetermined amount of catalyst; and
the initial catalyst replacement ratio is a ratio of the predetermined amount of catalyst to the total catalyst.
8. An apparatus for determining a fischer-tropsch catalyst replacement strategy in a reactor on-the-fly, the fischer-tropsch catalyst replacement strategy comprising replacement intervals and replacement proportions for replacing fischer-tropsch catalyst in the reactor, the apparatus comprising:
the acquisition module is used for acquiring an initial catalyst replacement interval and an initial catalyst replacement proportion;
a determination module to perform the following operations:
determining a catalyst proportion corresponding to the operation duration based on a pre-established catalyst proportion distribution model, the initial catalyst replacement interval and the initial catalyst replacement proportion;
determining the activity of the catalyst corresponding to the operation duration based on a pre-established catalyst deactivation model;
determining a catalyst integrated activity corresponding to the operation time period based on the catalyst activity, the catalyst ratio, the initial catalyst replacement interval, and the initial catalyst replacement ratio; and
determining a loss ratio based on a pre-established loss model and the comprehensive activity of the catalyst; and
and the adjusting module is used for adjusting the catalyst replacement interval and the catalyst replacement proportion according to the loss ratio so as to determine the replacement interval and the replacement proportion for the Fischer-Tropsch catalyst in the replacement reactor.
9. A machine readable storage medium having stored thereon instructions for causing a machine to perform the method for determining a fischer-tropsch catalyst replacement strategy in a reactor on-the-fly of any one of claims 1 to 7.
10. A processor configured to run a program, wherein the program when executed is configured to perform the method of any one of claims 1 to 7 for determining a fischer-tropsch catalyst replacement strategy for a reactor on the fly.
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