CN101670253A - Methods and apparatus for exothermic catalystic process - Google Patents

Abstract

Methods and apparatus for carrying out exothermic catalytic process are provided. In an implementation, an exothermic catalytic process is conducted in a catalyst bed having a plurality of sections, wherein the plurality of sections and reaction conditions are configured such that a maximum temperature in each of at least two of the plurality of sections is equal to a predetermined temperature orwithin a predetermined temperature range to obtain higher yield.

Description

Implement the method and the device of heat release Catalytic processes

[technical field]

The application relates to method and the device of implementing the heat release Catalytic processes.

[background technology]

Fischer-Tropsch is synthetic to be to be the technical process of the synthetic liquid fuel based on hydrocarbon products of raw material with the synthesis gas, and being mainly used in that indirect coal liquefaction (ICL) or natural gas synthetic oil (GTL) etc. relate to the synthesis gas is in each intermediate item of raw material production liquid fuel.With regard to response feature, Fischer-Tropsch synthesizes strong exothermal reaction, and its reaction speed improves with the rising of reaction temperature, if reaction temperature surpasses a critical-temperature, will temperature runaway take place or catalyst burns.So commercialization Fischer-Tropsch synthesizer needs good cooling system, and operate under the well-designed operating condition of a cover, in the hope of obtaining maximum output.

The catalytic bed of conventional fixed bed Fischer-Tropsch synthesis device is loaded single catalyst equably.In course of reaction, the temperature of catalytic bed flows to raise rapidly earlier along reactant and reduces then, thereby forms a temperature peak at an ad-hoc location, and this position is called as " focus ".Because near the temperature of the part the focus is the highest, (reaction activity) is the highest for its reactivity, and other parts are lower because of temperature, and its reactivity is also corresponding lower.As described above, too high reaction temperature can cause temperature runaway, has limited the synthetic output of Fischer-Tropsch so can not be higher than the temperature peak of critical-temperature.In addition, because the temperature axial gradient of catalytic bed is bigger, conducting heat does not reach optimization.Obviously, also have bigger space to promote the synthetic output of Fischer-Tropsch, in other words, also have bigger space to improve the synthetic economic benefit of Fischer-Tropsch.

For indirect Coal Liquefaction Project or natural gas synthetic oil project, the expense that is used for the air separation unit of synthesis gas production stage accounts for the large percentage of gross investment.If but directly adopted air to carry out synthesis gas production, with the content that makes synthesis gas in the product low excessively (with the natural gas synthetic oil project would be example, and synthesis gas content is approximately 60% in the product, and nitrogen content is approximately 40%).This synthesis gas is used for Fischer-Tropsch when synthetic, and major part is nitrogen in the synthetic tail gas of Fischer-Tropsch, significantly increase as if carrying out the recycling energy consumption that will make to tail gas, and the major part of these energy consumptions all is wasted in the circulation to nitrogen.So, be generally tail gas not to be carried out recyclingly in the fischer-tropsch synthesis process of unstripped gas with the synthesis gas that directly makes with air, but exhaust combustion is generated electricity.But so, the effective rate of utilization of synthesis gas (synthesis gas is converted into the ratio of liquid form product) has just reduced.

(the Fischer-Tropsch device that provides such as Syntroleum company) adopt the air preparing synthetic gas exactly, and tail gas is used to combustion power generation in more existing miniaturization Fischer-Tropsch synthesizers.Because it is recycling that it does not carry out tail gas, if the conversion per pass of its Fischer-Tropsch synthesizer can not reach higher level, then the effective rate of utilization of its synthesis gas is lower, can influence its economic benefit.

In sum, be necessary to provide higher Fischer-Tropsch synthesizer of a kind of yield and the high Fischer-Tropsch synthesizer of a kind of conversion per pass, to increase economic efficiency.And this device also can be used for other heat release Catalytic processes.

[summary of the invention]

Synthetic and similar heat release Catalytic processes can improve yield by the mean temperature that improves catalytic bed for Fischer-Tropsch.The application's a embodiment is by catalytic bed is divided into multistage, and makes at least two sections maximum temperature equal predetermined first temperature or be in predetermined first temperature range, improving the mean temperature of catalytic bed, and then improves yield.

In one embodiment, first temperature is the critical-temperature of this heat release Catalytic processes.

In another embodiment, first temperature is being for guaranteeing under the prerequisite that this heat release Catalytic processes normally carries out, and is accessible near the temperature of the critical-temperature of this heat release Catalytic processes under the concrete operations condition.

In another embodiment, first temperature is being for guaranteeing under the prerequisite that this heat release Catalytic processes normally carries out, and accessible this heat release Catalytic processes that makes has the temperature of high yield under the concrete operations condition.

In one embodiment, first temperature range is for being peak with the critical-temperature of this heat release Catalytic processes, with the rational minimum temperature span that can control under the concrete operations condition temperature range that is span.

In another embodiment, first temperature range is for guaranteeing under the prerequisite that this heat release Catalytic processes normally carries out, with accessible under the concrete operations condition be peak near the temperature of the critical-temperature of this heat release Catalytic processes, with the rational minimum temperature span that can control under the concrete operations condition temperature range that is span.

In another embodiment, first temperature range is for guaranteeing under the prerequisite that this heat release Catalytic processes normally carries out, with under the concrete operations condition accessible make this heat release Catalytic processes have the temperature of high yield is a peak, with the rational minimum temperature span that can control under the concrete operations condition temperature range that is span.

It is listed that first temperature and first temperature range are not limited to above embodiment.

The application's one side provides a kind of reactor that is used for a heat release Catalytic processes, and it comprises reaction tube and is located in the described reaction tube and flows to the catalytic bed of extending along reactant.Wherein, this catalytic bed flows to along reactant and is provided with a plurality of sections, these a plurality of sections are by a predetermined way setting, this predetermined way can obtain by simulation or experiment, its objective is to make when this reactor is used to implement described heat release Catalytic processes wherein have at least maximum temperature in two bed sections to equal a predetermined temperature or be within the predetermined temperature range.

Equaling a predetermined temperature can be to approximate this predetermined temperature greatly, can consider the error in the actual enforcement.

In one embodiment, the catalytic activity difference of the catalysis material that loaded of the bed section that is adjacent of the catalytic activity of the catalysis material that loaded of arbitrary described bed section.

In one embodiment, the catalytic activity that flows to the catalysis material that the bed section in downstream loaded along reactant is higher than the catalytic activity of the catalysis material that the bed section of upstream loaded.

In one embodiment, described heat release Catalytic processes is implemented under a predetermined reaction condition, and this predetermined reaction condition is provided with and described a plurality of sections are based on.

In one embodiment, described predetermined reaction condition comprises the reactant air speed.

In one embodiment, described heat release Catalytic processes is a fischer-tropsch synthesis process.

In one embodiment, the temperature peak of maximum temperature in this section, forming of described bed section.

The application's the method that a kind of enforcement one heat release Catalytic processes is provided on the other hand, it may further comprise the steps: form a catalytic bed in a reaction tube, this catalytic bed comprises a plurality of sections; And in described reaction tube, implement described heat release Catalytic processes, make the maximum temperature of at least two bed sections equal a predetermined temperature respectively or be within the predetermined temperature range.

In one embodiment, the step that forms catalytic bed also comprises a regulating step, and the catalytic activity of regulating the catalysis material that fills in each section is or/and reaction condition.

In one embodiment, described regulating step is further comprising the steps of: obtain catalytic bed temperature and distribute; Described Temperature Distribution and a predetermined temperature or a predetermined temperature range are compared; And regulate the catalytic activity of catalysis material of corresponding bed section according to described comparison or/and reaction condition.

The application's another aspect provides a kind of computer readable medium, store and to be made this processor implement the instruction of the method for a design heat release Catalytic processes after the computer processor execution, this method is provided with the distribution of calculating acquisition one catalytic bed temperature according to catalytic bed setting of setting and reaction condition, and the catalytic bed temperature distribution that is obtained is compared with first temperature of being scheduled to or first temperature range of being scheduled to.If distributing, the catalytic bed temperature that obtains is not inconsistent the first predetermined temperature conditions of unification, then the catalytic bed setting of regulating described setting according to comparative result is or/and the reaction condition setting, and the above step of repetition is set until the catalytic bed temperature distribution that obtains to meet first temperature conditions according to catalytic bed setting after regulating and reaction condition.Catalytic bed described here is used to be arranged in the reaction tube, and this catalytic bed setting comprises the bed hop count amount of this catalytic bed and the catalytic activity of the catalysis material that each section is loaded etc.

In one embodiment, first temperature conditions is that the maximum temperature of at least two bed sections of catalytic bed equals first temperature, perhaps is within described first temperature range.

In another embodiment, first temperature conditions is that the maximum temperature of at least two bed sections of previously selected catalytic bed equals first temperature, perhaps is within described first temperature range.

In one embodiment, described reaction condition setting comprises the reactant air speed.

In one embodiment, described reaction condition setting comprises the reactant composition.

In one embodiment, described reaction condition setting comprises the reaction tube wall temperature.

In one embodiment, described reaction condition setting comprises pressure.

In one embodiment, described catalytic bed setting also comprises the catalytic bed size.

The application's another aspect provides a kind of reactor assembly that is used for the heat release Catalytic processes, and this reaction system comprises first reactor and second reactor.Wherein, second reactor is connected with first reactor and is made product and residual reactant to the output of small part first reactor can be imported into second reactor.First and second reactors comprise first and second reaction tubes and first and second heat-exchange devices respectively, and the external temperature that is respectively applied for first and second reaction tubes is controlled at T1 and T2, and wherein, T2 is higher than T1.Wherein, be respectively equipped with first and second catalytic beds in first and second reaction tubes, first catalytic bed flows to along reactant and is provided with a plurality of first section, make the reaction compartment in this first reaction tube be divided into a plurality of first conversion zones, the catalysis material that these first section loaded makes when this reactor assembly is used to implement described heat release Catalytic processes, has at least the maximum temperature of two first conversion zones to equal first a predetermined temperature in described a plurality of first conversion zones or is within the first predetermined temperature range.

In one embodiment, the catalytic activity difference of two any adjacent first sections.

In one embodiment, the catalytic activity of the catalysis material that loads of first section of corresponding described at least two first conversion zones is different.

In one embodiment, the catalytic activity that flows to the catalysis material that first section in downstream load along reactant is higher than the catalytic activity of the catalysis material that first section of its upstream load.

In one embodiment, can comprise diluent in the catalysis material that a plurality of first section are loaded, the ratio difference of diluent in the catalysis material that each first section is loaded, thus make the catalytic activity difference of the catalysis material that each first section loads.

In one embodiment, described second catalytic bed flows to along reactant and is provided with a plurality of second section, and making the reaction compartment in this second reaction tube be divided into a plurality of second conversion zones, catalysis material that the maximum temperature that described a plurality of second conversion zones have two second conversion zones at least when this reactor assembly is used for implementing described heat release Catalytic processes is loaded because of described a plurality of second section and described T2 equal first a predetermined temperature or are within the second predetermined temperature range.

In one embodiment, the catalytic activity difference of two any adjacent second sections.

In one embodiment, the catalytic activity of the catalysis material that loads of at least two second sections of corresponding at least two second conversion zones is different.

In one embodiment, the catalytic activity that flows to the catalysis material that second section in downstream load along reactant is higher than the catalytic activity of the catalysis material that second section of upstream load.

In one embodiment, can comprise diluent in the catalysis material that a plurality of second section are loaded, the ratio difference of diluent in the catalysis material that each second section is loaded, thus make the catalytic activity difference of the catalysis material that each second section loads.

In one embodiment, the maximum temperature of first conversion zone and second conversion zone is respectively the temperature peak that forms in first conversion zone of correspondence and second conversion zone.

In one embodiment, between first reactor and second reactor, be provided with one first product gathering-device, collect the liquid product of part by the output of first reaction tube.

The application's another aspect provides a kind of method that is provided with or designs a heat release Catalytic processes, may further comprise the steps: first reactor and corresponding reaction condition are set; Second reactor and corresponding reaction condition are set, described second reactor is connected with first reactor, make the material stream of exporting to small part first reactor be transfused to the reaction raw materials of second reactor as second reactor, first and second reactors comprise first and second reaction tubes respectively and are located at the first and second interior catalytic beds of first and second reaction tubes respectively that first catalytic bed comprises a plurality of first section that is filled with catalysis material; The catalysis material that loads according to each first section and the reaction condition of first reactor obtain the Temperature Distribution of first catalytic bed; If the Temperature Distribution of first catalytic bed that is obtained is inconsistent the first predetermined temperature conditions of unification, adjust catalysis material that first section load or/and the reaction condition of first reactor; If the Temperature Distribution of first catalytic bed that is obtained symbol and the described first predetermined temperature conditions obtain the flow that the material by the output of first reactor flows and form; According to obtained by the flow of the material stream of first reactor output and form, catalysis material that second catalytic bed is loaded and the reaction condition of second reactor, obtain the Temperature Distribution of second catalytic bed; If the Temperature Distribution of second catalytic bed that is obtained is inconsistent the second predetermined temperature conditions of unification, adjust catalysis material that second section load or/and the reaction condition of second reactor.

In one embodiment, first temperature conditions can equal first a predetermined temperature or be positioned at first a predetermined temperature range for the maximum temperature of first section of predetermined first quantity, and wherein, first quantity is more than or equal to two; First temperature conditions also can equal first temperature at least or be positioned at first temperature range for the maximum temperature of preassigned two first sections; First temperature conditions can also equal first temperature at least or be within first temperature range for the maximum temperature of two first sections.

In one embodiment, second temperature conditions is that the maximum temperature of second catalytic bed equals second a predetermined temperature or is positioned at second a predetermined temperature range.

In another embodiment, second catalytic bed comprises a plurality of second section that is filled with catalysis material, second temperature conditions is that the maximum temperature of second section of predetermined second quantity equals second a predetermined temperature or is in the second predetermined temperature range, wherein, second quantity is more than or equal to two; Second temperature conditions also can equal second temperature at least or be in second temperature range for the maximum temperature of preassigned two second sections.

In one embodiment, the reaction condition of adjusting second reactor comprises the external temperature of adjusting second reaction tube.

The application's another aspect provides a kind of method of enforcement one heat release Catalytic processes, may further comprise the steps: form one first catalytic bed in one first reaction tube of one first reactor, first catalytic bed comprises a plurality of first section; Form one second catalytic bed in one second reaction tube of one second reactor, second reactor is connected with described first reactor, so that the material stream of small part first reactor output is as reaction raw materials; In first reactor and second reactor, implement described heat release Catalytic processes, make the Temperature Distribution of first catalytic bed meet first a predetermined temperature conditions, make the Temperature Distribution of second catalytic bed meet second a predetermined temperature conditions.

In one embodiment, first temperature conditions can be that the maximum temperature of first section of first quantity of being scheduled to equals first a predetermined temperature or is positioned at first a predetermined temperature range, and wherein, first quantity is more than or equal to two; First temperature conditions also can be that the maximum temperature of preassigned at least two first sections equals first temperature or is positioned at first temperature range; First temperature conditions can also be that the maximum temperature of at least two first sections equals first temperature or is within first temperature range.

In one embodiment, second temperature conditions is that the maximum temperature of second catalytic bed equals second a predetermined temperature or is positioned at second a predetermined temperature range.

In another embodiment, second catalytic bed comprises a plurality of second section that is filled with catalysis material, second temperature conditions is that the maximum temperature of second section of predetermined second quantity equals second a predetermined temperature or is in the second predetermined temperature range, wherein, second quantity is more than or equal to two; Second temperature conditions also can be that the maximum temperature of preassigned at least two second sections equals second temperature or is in second temperature range.

[description of drawings]

Fig. 1 is the schematic diagram of a segmented reactor.

Fig. 2 is a catalytic bed temperature curve map example.

Fig. 3 is the flow chart of the method for an enforcement heat release Catalytic processes.

Fig. 4 one is provided with the flow chart of the method for catalytic bed.

Fig. 5 one is used to be provided with the functional block diagram of the computer system of heat release Catalytic processes.

Fig. 6 is the flow chart of the method for an optimization heat release Catalytic processes.

Fig. 7 is the catalytic bed temperature curve map of example one.

Fig. 8 is the catalytic bed temperature curve map of example two.

Fig. 9 is the catalytic bed temperature curve map of example three.

Figure 10 is the catalytic bed temperature curve map of example four.

Figure 11 is the temperature profile of embodiment 7A and 7B in the example seven.

Figure 12 is the temperature profile of embodiment 8A and 8B in the example eight.

Figure 13 is the temperature profile of embodiment 9A and 9B in the example nine.

Figure 14 is the structural representation of a reaction system.

Figure 15 is the structural representation of a reaction system.

Figure 16 one is provided with the flow chart of the method for heat release Catalytic processes.

Figure 17 is the example I in the example ten, first catalytic bed of J, K and the temperature profile of second catalytic bed.

Figure 18 is the flow chart of the method for an enforcement heat release Catalytic processes.

[specific embodiment]

Below will be by a plurality of embodiment to the applicant invented The type reactor is described in detail, and when disclosing it and being used for the heat release Catalytic processes, than the lifting of traditional reactor at aspects such as conversion per pass and space-time yields.

Fig. 1 has showed a kind of heat release Catalytic processes (synthetic such as Fischer-Tropsch) of being used for Type reactor 100.Reactor 100 comprises that a reaction tube 110 and is located at the catalytic bed 120 in the reaction tube 110.Reaction tube 110 is provided with at least one input port 112, with reactant input reactor 100.Reaction tube 110 also comprises an output port 114, with product and residual reactant output-response device 100.Catalytic bed 120 is extended along the central shaft A-A ' of reaction tube 110, comprise one first end 122 near input port 112, near one second end 124 of output port 114, and be located at a plurality of section S1, S2...Sn that are provided with continuously along direction F between first end 122 and second end 124.

In one embodiment, when bed section S1, S2...Sn are configured to carry out a heat release Catalytic processes, make the maximum temperature of each section equal first temperature of being scheduled to or be in first a predetermined temperature range.

When Fig. 2 is n=8, an example of the temperature profile of reactor 100 catalytic bed central shaft A-A '.Fig. 2 represents this position of point on central shaft A-A ' with catalytic bed 120 capacity (Net Volume) that 110 central shaft A-A ' go up certain catalyst that can load between a bit from first end 122 to reaction tube.Certainly, the radially mean temperature of 110 tube walls also can be used for representing the temperature distribution state of catalytic bed 120 from central shaft A-A ' to reaction tube.As shown in Figure 2, each section S1, S2...S8 have a maximum temperature T _Max, a bed section pairing maximum temperature of S1 to S7 and a predetermined temperature T _cBetween difference be positioned within the preset range Δ T.

In one embodiment, for obtaining desirable temperature curve (temperature curve as shown in Figure 2, in a heat release catalytic process, the difference of the maximum temperature of at least two bed sections and a predetermined temperature is in the preset range), the active difference of at least two catalysis materials that it loaded among described a plurality of section S1, the S2...Sn.In one embodiment, at least two bed section fillings are with the of the same race catalyst of same inert substance with different thinner ratio dilutions, so that the catalysis material that these at least two bed sections are loaded has different catalytic activitys.In another embodiment, the catalyst of at least two bed section fillings is different, so that the catalytic activity of the catalysis material that these at least two bed sections are loaded is different.In another embodiment, at least two two or more catalyst that the filling of bed section mixes in varing proportions are so that the catalytic activity of the catalysis material that these at least two bed sections are loaded is different.In another embodiment, at least two bed sections are loaded catalyst of the same race, in these at least two bed sections, different bed sections are diluted described catalyst with different diluents, or dilute with the catalyst of different thinner ratios to different bed sections with identical diluent, so that the catalytic activity of the catalysis material that these at least two bed sections are loaded is different.

In one embodiment, catalytic bed 120 is configured to its catalytic activity and flows to along reactant

Improve.

In one embodiment, one heat release Catalytic processes carries out under a predetermined input flow rate and a predetermined input component ratio, and the catalytic activity of catalytic bed 120 each section S1, S2...Sn according to should predetermined input flow rate and the predetermined component ratio of importing be provided with one of at least.In another embodiment, require this heat release Catalytic processes to reach an intended conversion rate, the catalytic activity of catalytic bed 120 each section S1, S2...Sn is provided with according to this intended conversion rate.

Fig. 3 has showed the flow chart of the method 300 of an enforcement heat release Catalytic processes.Please join Fig. 3, method 300 may further comprise the steps: form catalytic bed (step 310) in reaction tube 110; And in reactor 100, implement the heat release Catalytic processes, the maximum temperature of each equals first a predetermined temperature in feasible at least two bed sections, perhaps is positioned at first a predetermined temperature range, just temperature curve as shown in Figure 2.

Fig. 4 has showed the flow chart of step 310.Please join Fig. 4, step 310 may further comprise the steps: choice reaction condition and catalytic bed setting (step 410).Wherein, reaction condition can comprise that all may influence the condition of temperature curve, selectivity or conversion ratio, such as input flow rate, input component ratio, reaction tube wall temperature, heat exchanger effectiveness, input temp, pressure, reflux ratio or the like.In one embodiment, other reaction conditions except that the reactant input flow rate are fixing.Wherein, catalytic bed setting can comprise the characteristic (such as activity, selectivity, structure, mass transfer and heat transfer property etc.) of catalyst, the characteristic of diluent and the thinner ratio of each section etc.In one embodiment, the parameter of other except that thinner ratio is fixing.The temperature curve (step 420) of the catalytic bed 120 that obtains a correspondence is set based on the reaction condition of selecting in the step 410 and catalytic bed.The temperature curve that is obtained by step 420 and a predetermined temperature or a predetermined temperature range are compared (step 430).Judge according to the comparing result that step 430 obtained whether this temperature curve meets a preassigned (step 440).Meet described preassigned if in step 440, judge the temperature curve that obtains by step 420, then the catalytic bed of selecting according to step 410 is arranged on and forms catalytic bed in the reaction tube 110, in reactor 100, implement the heat release Catalytic processes according to the reaction condition that step 410 is selected, to obtain to meet the catalytic bed temperature curve (step 450) of described preassigned.Do not meet described preassigned if in step 440, judge the temperature curve that obtains by step 420, then skip to step 410 and reselect reaction condition and catalytic bed setting, in step 420, to obtain corresponding temperature curve.Can repeating step 410 to step 440 until the temperature curve that obtains to meet described preassigned.

In one embodiment, preassigned can be that the maximum temperature of the bed section of predetermined quantity equals predetermined temperature or is positioned at predetermined temperature range.

In one embodiment, preassigned can be that the maximum temperature of preassigned bed section equals predetermined temperature or is positioned at predetermined temperature range.

In one embodiment, can automatically perform step 410 to step 440 by computer control.

In one embodiment, utilize computer Simulation calculation to obtain temperature curve in the step 420.With reaction condition, catalytic bed setting and other relevant parameters input computer, utilize pre-designed computation model to calculate correlated results, such as Temperature Distribution of conversion ratio, yield and catalytic bed or the like.

In another embodiment, in the step 420 by experiment to obtain temperature curve.The filling catalysis material is measured catalytic bed temperature distribution and conversion ratio etc. then to form a catalytic bed and to implement the heat release Catalytic processes in a reactor.

In one embodiment, the part steps of method 300 or Overall Steps can be realized by computer (as the computer system 500 that Fig. 5 showed).Please join Fig. 5, computer system 500 can comprise a processor (such as central processing unit) 501, a storage device 503, input/output device 511,513,515 and 517 and system bus 510, described each parts are connected with system bus 510, and carry out exchanges data by system bus 510.

Storage device 503 can comprise a random access storage device (RAM) 503a and a computer-readable storage medium 503b, wherein, storage medium 503b has stored a computer program 505, such as can be used for simulating the heat release Catalytic processes by inferior Shengong department exploitation

The development and use of this computer program Windows 2003 operating systems, Excel and the VisualStudioC++ of Microsoft, some have also been used at " Numerical Recipes in C " (William H.Press, Saul A.Teukolsky, William T.Vetterling and Brian P.Flannery, Cambridge UniversityPress) the middle algorithm of describing.Storage medium 503b can be the part or all of of hard disk, portable hard disk, laser disc, memory stick (memory stick) etc.

Please join Fig. 6, after computer program 505 is carried out by processor 501, will make processor 501 carry out the method 600 that may further comprise the steps: to receive a catalytic bed setting and reaction condition configuration (step 610).Temperature Distribution (step 620) when going out this catalytic bed and under this catalytic bed setting and reaction condition, carry out the heat release Catalytic processes according to this catalytic bed setting and reaction condition analog computation.In one embodiment, catalytic bed setting has been specified the quantity of the included bed section of catalytic bed, and the catalytic activity of each section, wherein, and the catalytic activity difference of two any adjacent bed sections.Method 600 is further comprising the steps of: will compare (step 630) by a Temperature Distribution and the predetermined temperature range that step 620 obtains.Judge according to the contrast of step 630 whether this Temperature Distribution meets a preassigned (step 640).If this Temperature Distribution meets this preassigned, then export this Temperature Distribution or/and other results (such as yield etc.) (step 650).If this Temperature Distribution does not meet this preassigned, then adjust at least one (step 660) in this catalytic bed setting and the reaction condition configuration, meet the Temperature Distribution of described preassigned then with this adjusted catalytic bed setting and reaction condition repeating step 620 to step 660 until acquisition.

In one embodiment, after computer program 505 is carried out by processor 501, processor 501 is compared a Temperature Distribution and a predetermined temperature range that obtains, and judge whether this Temperature Distribution meets a preassigned, regulate catalytic bed setting and reaction condition according to this contrast then, that is to say that this heat release Catalytic processes can carry out Automatic Optimal by computer.

In one embodiment, the step 420 in the method 300 or/and the step 620 in the method 600 can realize by computer simulation.At first, in computer, set up the pseudo-homogeneous phase model (pseudohomogenous model) of this technology, in this model, the reactant concentration C of catalytic bed level _A ^BAnd temperature is used as dynamic variable, and the characteristic of catalyst and diluent is then as internal factor (internal forces).The core of this model is based on above variable, corresponding each reactant, build on mass-conservation equation and energy conservation equation in the cylindric space of fixed bed reactors of a simulation.

Suppose that catalytic bed is around the central shaft symmetry, that is to say at arbitrary axial location, catalytic bed is identical with equidistant all reaction conditions of having a few of central shaft (comprising the linear velocity of temperature, pressure, reactant concentration, various materials etc.), and so described mass-conservation equation and energy conservation equation have just become the two-dimentional partial differential equation (partial differential equations) of following parameter: reaction rate r (C _A ^B, T) and series of parameters as flow velocity U vertically _z(cm/s), specific heat C _p(specific heat), effective diffusion cofficient D _e(cm2/s) (effective diffusivity), thermal conductivity k _e(k _EzBe axial thermal conductivity, k _ErBe radial thermal conductivity) (thermal conductivity), reaction heat Δ H (kJ/mo1), reactant concentration ρ _g(density ofreactant), catalytic bed inner catalyst density p _B(density of catalyst in packed bed), heat exchange coefficient U _w(J/scm ²K) (heat transfer coefficient), (please join " Continuity and EnergyEquations " the chapters and sections 11.7.2 that is shown by Gilbert F.Froment and Kenneth B.Bischoff, and John Wiley ﹠amp as following equation 1 and equation 2; " Chemical ReactorAnalysis And Design " nineteen ninety second edition that Sons, Inc. publish, the content of these two works be cited and as a part of content of the application).

$D_{\mathrm{er}}(\frac{{\&PartialD;}^2{C}_A^B}{{\&PartialD;\mathrm{<figure-callout\; id="2"\; label="r"\; filenames="A2008101890490045H1.png,A2008101890490048H1.png"\; state="\{\{state\}\}">r</figure-callout>}}^2}+\frac{1}{r}\&CenterDot;\frac{\&PartialD;C_A^B}{\&PartialD;r})+D_{\mathrm{ez}}\frac{{\&PartialD;}^2{C}_A^B}{{\&PartialD;z}^2}-U_z\frac{\&PartialD;C_A^B}{\&PartialD;z}+{\mathrm{\&rho;}}_s\&CenterDot;r_A^{\&prime;}=0---\left(1\right)$

Wherein, r ' _AReaction rate (reaction rate percatalyst weight) for the unit mass catalyst of reactant A; ρ _sBe the density of catalyst in the catalyst granules (catalyst volume density incatalyst pellet).

$k_{\mathrm{er}}(\frac{{\&PartialD;}^{2}T}{{\&PartialD;\mathrm{<figure-callout\; id="2"\; label="r"\; filenames="A2008101890490045H1.png,A2008101890490048H1.png"\; state="\{\{state\}\}">r</figure-callout>}}^2}+\frac{1}{r}\&CenterDot;\frac{\&PartialD;T}{\&PartialD;r})+k_{\mathrm{ez}}\frac{{\&PartialD;}^{2}T}{{\&PartialD;z}^2}-U_z\&CenterDot;C_p^{\mathrm{mol}}\&CenterDot;\frac{{\&PartialD;T}_A}{\&PartialD;z}+(-{\mathrm{\&Delta;H}}_{\mathrm{rx}}){\mathrm{\&rho;}}_s\&CenterDot;r_A^{\&prime;}=0---\left(2\right)$

Wherein, T is a temperature; Δ H _RxBe reaction heat (reaction heat) that subscript " rx " is represented a certain reaction; Subscript in the above equation " A " is represented a certain reactant.

Can utilize with downstream condition solve an equation 1 with equation 2:

$C_A^B=C_{A0}^B,$ T=T ₀(work as z=0,0≤r≤R _t, wherein, z is the position that flows to along reactant, R _tBe tube inner diameter)

$\frac{{\&PartialD;C}_A^B}{\&PartialD;r}=0$ (work as z=0, r=R _t, any position that flows to along reactant)

$\frac{\&PartialD;T}{\&PartialD;r}=0$ (working as r=0, any position that flows to along reactant)

$\frac{\&PartialD;T}{\&PartialD;r}=-\frac{U_w}{k_{\mathrm{er}}}(T_R-T_w)$ (work as r=R _t, any position that flows to along reactant)

Wherein, T _RBe the temperature between catalytic bed border and the reaction tube, T _wTemperature for the reaction tube wall.

For separating above two-dimentional partial differential equation, need earlier at mass-conservation equation (equation 3) to separate following catalyst particles grade under the downstream condition:

$\frac{d^2{\mathrm{<figure-callout\; id="2"\; label="C\; A\; dr"\; filenames="A2008101890490045H1.png,A2008101890490048H1.png"\; state="\{\{state\}\}">C</figure-callout>}}_A}{{\mathrm{dr}}^{}}+\frac{2}{r}\&CenterDot;\frac{{\mathrm{dC}}_A}{\mathrm{dr}}+\frac{{\mathrm{\&rho;}}_s}{D_e}\&CenterDot;r_A^{\&prime;}=0---\left(3\right)$

Boundary condition:

${\frac{{\mathrm{dC}}_A}{\mathrm{dr}}|}_{r=0}=0$

${C_A|}_{r=R}=C_A^B$ (R is the catalyst granules radius)

$r_A=\&Integral;{\mathrm{dr}}_A={\&Integral;r}_A^{\&prime;}\&CenterDot;\mathrm{dW}={\&Integral;}_0^R{r}_A^{\&prime;}[T,C_A]\&CenterDot;{\mathrm{\&rho;}}_s\&CenterDot;4\&CenterDot;\mathrm{\&pi;}\&CenterDot;{\mathrm{<figure-callout\; id="2"\; label="r"\; filenames="A2008101890490045H1.png,A2008101890490048H1.png"\; state="\{\{state\}\}">r</figure-callout>}}^2\&CenterDot;\mathrm{dr}$

In one embodiment, reaction is considered to occur in the surface, inside of common porous catalyst particle.Therefore, the r in the equation 1 _ACan be expressed as C _AEquation r _A=r _A(C _A, T).Under the hypothesis of pseudo-homogeneous phase, can C _A ^BSolve an equation 3 to obtain CONCENTRATION DISTRIBUTION (intra-pelletconcentration profile) in the particle as boundary condition.In one embodiment, suppose the thermal conductivity infinity of catalyst granules, temperature is even in the particle, and so, the energy conservation equation of catalyst particles grade can omit.Then, utilize r in the particle _AMean value solve an equation 1 and equation 2.For spherical particle, can adopt spherical coordinate system (spherical coordinates).For first order reaction, can find closed form to separate (closed formsolutions).

Then, determine the reaction rate law (rate law) of reaction network (reaction network) and corresponding reaction, related parameter values can be obtained from thermodynamic database or paper or experimental data.

Numerical solution (numerical method) can be used for separating the catalytic bed level equation and the catalyst particles grade equation of described coupling.As know known to this operator, shooting method (shooting method) can be used for separating mixed boundary condition (as catalyst particles grade equation), and the Crank-Nicholson algorithm can be used for separating partial differential equation (as catalytic bed level equation).

$\mathrm{\&eta;}=\frac{\underset{\&OverBar;}{{r^{\&prime;}}_A}}{r_A^{\&prime;}\left(C_A^B\right)}---\left(4\right)$

In one embodiment, can calculate defined efficiency factor η in the equation 4 by the reaction rate law of separating individual particle earlier, and, be stored in a database or the form such as the efficiency factor η of temperature, pressure etc. with the corresponding differential responses condition of gained.When finding the solution the equation of bed, just can directly from described database or form, read efficiency factor, thereby save the computing time of finding the solution particle-bed coupled wave equation formula significantly.

Before separating catalyst particles grade equation, need to obtain earlier the reaction rate law of corresponding reaction.In one embodiment, the laboratory scale experimental result of relevant conversion at next reactant of special catalyst effect (such as the conversion of carbon monoxide in fischer-tropsch synthesis process) is used to calculate the parameter of reaction rate law, such as reaction rate constant (rate constant), part and general reaction progression (partialand overall orders of reaction), apparent activation energy (apparent activation energy) and heat exchange coefficient (heat transfer coefficient) etc., then, calculate the reaction rate law of catalyst particles grade.Then, can utilize the reaction rate law of catalyst particles grade to calculate the reaction rate law of catalytic bed level.At last, just can obtain a model that is used to simulate a plant-scale reaction system.

In following example, this model is used to simulation or/and optimize a heat release Catalytic processes, wherein this heat release Catalytic processes comprises enforcement in the catalytic bed of the individual bed section of n (n for greater than 1 integer) one, wherein, each Duan Youyi catalytic activity factor, these catalytic activity factors are the catalytic activity index of the corresponding bed section catalyst that is loaded.In simulation, the counterpart of two adjacent bed section adjoiners is considered to have identical material concentration and Temperature Distribution.For a selected catalytic bed setting, after having determined reaction condition, reaction-ure conversion-age (reactant conversion), yield (yield) and catalytic bed temperature distribute and can be obtained by this modeling.Based on the result that this simulation obtained, can adjust the catalytic bed setting or/and reaction condition disposes, and then obtain new analog result based on this adjusted catalytic bed setting and reaction condition configuration.Therefore, can utilize this model optimization catalytic bed setting and reaction condition to be configured to obtain more excellent yield or/and other target variables, such as conversion ratio, selectivity etc.

Below will be that example describes with the fischer-tropsch synthesis process.Fischer-tropsch synthesis process comprises following reaction:

Alkane is synthetic: (2n+1) H ₂+ nCO → C _nH _2n+2+ nH ₂O, n=1,2,3 ...

Alkene is synthetic: 2nH ₂+ nCO → C _nH _2n+ nH ₂O, n=2,3...

Water-gas shift reaction: CO+H ₂O → CO ₂+ H ₂

Following example one to example four be based on the listed simplification of following table one reaction network, the reaction rate law of corresponding reaction is also listed.

Table one

??C 2+Hydro carbons is synthetic	?2H 2+CO→1/n?C nH 2n+H 2O，n＝2，3...
		Methane is synthetic	?3H 2+CO→CH 4+H 2O
The reaction rate law	?r CO＝-k 0·exp(-Ea/RT)·P H2

Wherein, P _H2Be hydrogen partial pressure, according to perfect gas law, it is relevant with the hydrogen molar concentration.R is a gas constant, equals 8.314Joule/ (Kmol).

Example one to the relevant parameter of example two as shown in Table 2.

In one embodiment, catalytic bed temperature distributes and conversion ratio is based on the listed reaction rate law of table three calculation of parameter gained, and these reaction rate law parameters can obtain by curve-fitting method according to experimental data as shown in Table 4.Experimental data shown in the table four is to load 0.45g, 0.6g, 0.9g and the 1.2g cobalt-base catalyst gained that experimentizes under 220 ℃, 230 ℃, 235 ℃ and 240 ℃ in 32 channel parallel reactor assemblies of inferior Shen science and technology research and development respectively.

Table two

Reactor inside diameter (in)	??0.5	Specific heat capacity (J/gK)
				Catalyst granules diameter (mm)	??0.25	??CO	??1.07
Diluent size (mm)	??0.25	??H 2	??14.5
				Temperature (℃)	??240	??H 2O	??2.80
Pressure (bar)	??30	??CH 4	??6.16
				Total flow (ml/min)	??37.5	Reaction heat Δ H (kJ/mol)	??160
Catalyst apparent density (g/ml)	??0.6	Effective diffusivity (cm 2/s)
				Catalytic bed height (cm)	??10	??CO	??10 -6
??H 2/CO	??2∶1	??H 2	??10 -5
				Heat exchange coefficient (J/scm 2·K)	??0.0025	??H 2O	??10 -6
Thermal conductivity (J/scmK)	??0.1	??CH 4	??10 -6

Table three

Reaction	??k 0_H 2(1/h)	??E a_H 2(kJ/mol)
			?C 2+Hydro carbons is synthetic	??2.60E+11	??100
Methane is synthetic	??7.45E+11	??110

Table four

Following example one to routine four-way is crossed simulation and carry out fischer-tropsch synthesis process in a catalytic bed is comprised the reactor of three isometric bed sections, show one by adjusting the catalytic bed setting or/and reaction condition the method for optimizing fischer-tropsch synthesis process is set.To example four, the reaction temperature upper limit is set at 250 ℃ in example one, and the reaction tube wall temperature is set to 240 ℃.

[example one]

Reactor in the example one adopts traditional catalytic bed setting, i.e. three active identical catalyst of bed section filling.The temperature distribution state that this catalytic bed is arranged on catalytic bed when carrying out fischer-tropsch synthesis process as shown in Figure 7.

Please join Fig. 7, the temperature of the catalytic bed in the example one flows to along reactant earlier and raises, and reaches a peak first section, reduces gradually then.As previously mentioned, fischer-tropsch synthesis process is strong heat release technology, and the heat that produces in the technology will cause temperature to raise, and the temperature that raises can accelerated reaction, thereby causes more heat to produce.Therefore, before first section temperature peaked, the temperature of catalytic bed flowed to rapidly along reactant and promotes.Simultaneously, because reaction consumes, the concentration of synthesis gas (Fischer-Tropsch synthesizes primary raw material) flows to rapidly along reactant and reduces, and is especially fast near the speed that its concentration of input port place reduces in catalytic bed.The consumption of reactant causes reaction speed to descend, and at the ad-hoc location of catalytic bed, catalytic bed temperature begins to descend, thereby has formed described temperature peak.Following table five has been showed the reaction condition and the reaction result of example one.

Table five

Active factors distributes	??1∶1∶1
		The CO conversion ratio	??37.7％
Synthesis gas content in the raw material	??69％
		Space-time yield	??0.0680mol/(gcat*h)

To adopt catalyst of the same race to simulate in example one to example four, wherein, undiluted this kind activity of such catalysts factor is set to 1.Active factors is indicated the activity of the catalysis material that each section loads, and also represents the degree that catalyst is diluted in the embodiment of diluent dilute catalyst simultaneously, accounts for 80% such as catalyst in the active factors 0.8 expression catalysis material, and diluent accounts for 20%.Example one adopts traditional catalytic bed setting, and its active factors was distributed as 1: 1: 1.

Space-time yield (Product Space Time Yield) representation unit is in the time, the amount of carbon atom that the product that produces under the effect of unit mass catalyst is contained.Total output (Total Productivity) is the interior contained amount of carbon atom of product that produces of representation unit time then, can be used for estimating the catalytic bed overall performance.Because example one to example four adopts specification reactor of the same race, (the hypothesis diluent has identical proportion with catalyst in simulation) identical in quality if of the catalyst that hypothesis example one catalytic bed to the example four is loaded, so relatively space-time yield and relatively coming to the same thing of total output, therefore, below with space-time yield as the index of estimating the catalytic bed overall performance.

In the synthetic facility of industrial Fischer-Tropsch, by adjusting synthesis gas flow (equaling total flow and the product of importing synthetic gas density in the material), the temperature peak of catalytic bed is equaled or, obtain the highest total output with this near a critical-temperature (setting of conventional catalyst bed has only a temperature peak).Keeping if further improve the synthesis gas flow, causing temperature runaway to cause catalyst to burn under the constant prerequisite of reaction time thereby the temperature peak of catalytic bed will surpass this critical-temperature.In example one, in order to make the temperature peak that results from first section be lower than a predetermined temperature, just must be controlled at the synthesis gas flow below one particular value accordingly, because synthesis gas is in the rapid consumption of first section, the concentration of synthesis gas is low excessively in three sections of second Duan Yudi, therefore, second section and the 3rd section just are not fully utilized.

A kind of method of heat release Catalytic processes yield that improves that the application provides on the one hand is for having the catalyst of different catalytically active in the different bed section filling of a catalytic bed, make the maximum temperature of these catalytic bed sections be in the predetermined temperature range, with the mean temperature of raising whole bed section, and then improve space-time yield.

In one embodiment, can be according to specifically considering, predetermined temperature is set at a certain value of subcritical temperature, with the security that guarantees to implement.

Example two

In example two, the catalytic bed of reactor is divided into three isometric bed sections along longitudinally, the catalysis material that has different catalytically active in the filling of different bed section, such as, first section loaded with the of the same race catalyst of diluent (such as quartz sand) with different ratios dilutions with second section, and the 3rd section loaded undiluted catalyst, thereby make these three bed sections form a temperature peak respectively, and these peak values equal a predetermined temperature respectively, and perhaps the difference with this predetermined temperature is within the preset range.Simultaneously, compared to example one, can also promote the concentration of synthesis gas in the input material.By the such catalytic bed setting and the raising of synthetic gas density, the whole yield of reactor internal reaction can be improved.In an embodiment of example two, adopt the catalyst identical with example one.Shown in following table six, load mixed uniformly 65% catalyst and 35% diluent first section, second section loaded mixed uniformly 80% catalyst and 20% diluent, the 3rd section loaded undiluted catalyst, the content of synthesis gas is under the reaction condition of 81% (and the peak that reactor can bear in the example one is 69%) in the input raw material, obtain the space-time yield of 0.0683mol/ (gcat*h), the Temperature Distribution of catalytic bed as shown in Figure 8.

Table six

Active factors distributes	??0.65∶0.8∶1
		The CO conversion ratio	??32.5％
Synthesis gas content in the raw material	??81％
		Space-time yield	??0.0683mol/(gcat*h)

Please join Fig. 8, the temperature peak of second section is higher than the temperature peak of first section, and the temperature peak of the 3rd section is higher than the temperature peak of second section and is higher than 250 ℃ of maximum permissible temperatures, and therefore, the 3rd section may temperature runaway take place or catalyst burns.According to result of calculation, more approaching but be no more than 250 ℃ of maximum permissible temperatures for the temperature peak that makes first to the 3rd section, need to improve the catalytic activity of first section and second section, reduce the synthesis gas content of importing in the raw material simultaneously.

Example three

On the result based on example two, more consistent for the peak temperature that makes first to the 3rd section, in example three, reduced the catalyst dilution rate of first section and second section.Following table seven has been showed the reaction condition and the reaction result of example three.

Table seven

Active factors distributes	??0.90∶0.95∶1
		The CO conversion ratio	??37.3％
Synthesis gas content in the raw material	??76.5％
		Space-time yield	??0.0742mol/(gcat*h)

Please join table seven, in example three, first section loaded mixed uniformly 90% catalyst and 10% diluent, and second section loaded mixed uniformly 95% catalyst and 5% diluent, and the 3rd section still loaded undiluted catalyst.The content of synthesis gas is 76.5% in the input raw material.Calculate as shown in Figure 9 Temperature Distribution and the space-time yield of 0.0742mol/ (gcat*h), this yield has promoted 9.12% than example one, has promoted 8.64% than example two.Please join Fig. 9, the temperature peak of first section is 250 ℃, and the temperature peak of second section is 249.5 ℃, and the temperature peak of the 3rd section is 249 ℃.More approaching for the temperature peak that makes first to the 3rd section, needs reduce the catalytic activity of first section and second section.If keeping the content of synthesis gas in the input raw material is 76.5% constant words, the catalytic activity that reduces by first section and second section can make the temperature peak of three sections of first Duan Zhidi reduce, therefore, in the catalytic activity that reduces by first section and second section, also should improve the content of synthesis gas in the input raw material.

Example four

In example four, compared to example three, the catalyst dilution rate of its first section and second section increases to some extent, and the content of synthesis gas promotes to some extent in its input raw material simultaneously.Following table eight has been showed the reaction condition and the reaction result of example four.

Table eight

Active factors distributes	??0.85∶0.90∶1
		The CO conversion ratio	??37％
Synthesis gas content in the raw material	??81％
		Space-time yield	??0.0779mol/(gcat*h)

Please join table eight, in example four, first section loaded mixed uniformly 85% catalyst and 15% diluent, and second section loaded mixed uniformly 90% catalyst and 10% diluent, and the 3rd section still loaded undiluted catalyst.The content of synthesis gas is set to 81% in the input raw material.Based on above-mentioned model, calculate as shown in figure 10 Temperature Distribution and the space-time yield of 0.0779mol/ (gcat*h), this yield has promoted 4.99% than example three, has promoted 14.56% than example one.Compare the lifting highly significant of its yield with the traditional catalytic bed setting described in the example one.Please join Figure 10, the temperature peak of first section is 250 ℃, and the temperature peak of second section is 249.5 ℃, and the temperature peak of the 3rd section is 249.8 ℃.

By above example as can be known, as long as the intrinsic activity (intrinsic activity) of known catalysts and the segmentation setting of catalytic bed just can utilize above-mentioned model to promote yield by optimizing Temperature Distribution.In one embodiment, the catalytic activity that can be by adjusting each section and the input flow rate of reactant are adjusted the Temperature Distribution of catalytic bed.

To example four,, in other embodiments, also can as the case may be catalytic bed be divided into more or less, isometric or not isometric bed section, in example two to optimize yield although catalytic bed all is divided into three isometric bed sections.

[example five]

If each section all forms a temperature peak, and each these temperature peak is equal to a predetermined temperature value or is positioned within the predetermined temperature range, and a catalytic bed is divided into many sections more so, and the mean temperature of this catalytic bed is just high more, correspondingly, its total output is just high more.But bed hop count amount is many more, increases bed hop count amount again, and the lifting of its total output is few more.Following examples will prove this rule.These embodiment still adopt parameter shown in the table two (except total flow), and employing and example one are to the identical catalyst of example four.Air speed that these embodiment adopted and result please ginseng tables nine.

In embodiment 5A, the undiluted catalyst of catalytic bed filling 1.2 grams, the content of synthesis gas is set at 61.5% in the input raw material.Based on above-mentioned model, catalytic bed forms a temperature peak and this temperature peak reaches 250 ℃, and space-time yield reaches 0.0352mol/ (gcat*h).

In embodiment 5B, catalytic bed is divided into two isometric bed sections, and loads the catalyst that dilutes by dilution rate shown in the table nine.When the content of synthesis gas was set at 66.1% in the input raw material, the temperature peak of each section was all enough near 250 ℃, and space-time yield reaches 0.0372mol/ (gcat*h), and compared to embodiment A, its space-time yield has promoted 5.68%.

In embodiment 5C, catalytic bed is divided into three isometric bed sections, and loads the catalyst that dilutes by dilution rate shown in the table nine.When the content of synthesis gas was set at 67.45% in the input raw material, the temperature peak of each section was all enough near 250 ℃, and space-time yield reaches 0.0376mol/ (gcat*h), and compared to embodiment A, its space-time yield has promoted 6.82%.

In embodiment 5D, catalytic bed is divided into four isometric bed sections, and loads the catalyst that dilutes by dilution rate shown in the table nine.When the content of synthesis gas was set at 68.15% in the input raw material, the temperature peak of each section was all enough near 250 ℃, and space-time yield reaches 0.0379mol/ (gcat*h), and compared to embodiment A, its space-time yield has promoted 7.67%.

In embodiment 5E, catalytic bed is divided into five isometric bed sections, and loads the catalyst that dilutes by dilution rate shown in the table nine.When the content of synthesis gas was set at 68.75% in the input raw material, the temperature peak of each section was all enough near 250 ℃, and space-time yield reaches 0.0381mol/ (gcat*h), and compared to embodiment A, its space-time yield has promoted 8.24%.

In embodiment 5F, catalytic bed is divided into six isometric bed sections, and loads the catalyst that dilutes by dilution rate shown in the table nine.When the content of synthesis gas was set at 69.15% in the input raw material, the temperature peak of each section was all enough near 250 ℃, and space-time yield reaches 0.0382mol/ (gcat*h), and compared to embodiment A, its space-time yield has promoted 8.53%.

In embodiment 5G, catalytic bed is divided into seven isometric bed sections, and loads the catalyst that dilutes by dilution rate shown in the table nine.When the content of synthesis gas was set at 69.28% in the input raw material, the temperature peak of each section was all enough near 250 ℃, and space-time yield reaches 0.0383mol/ (gcat*h), and compared to embodiment A, its space-time yield has promoted 8.81%.

In embodiment 5H, catalytic bed is divided into eight isometric bed sections, and loads the catalyst that dilutes by dilution rate shown in the table nine.When the content of synthesis gas was set at 69.35% in the input raw material, the temperature peak of each section was all enough near 250 ℃, and space-time yield reaches 0.0384mol/ (gcat*h), and compared to embodiment A, its space-time yield has promoted 9.09%.

Table nine

As seen from the above embodiment, when the temperature peak of each section is equal to a predetermined temperature value or is positioned within the predetermined temperature range, a catalytic bed is divided into many sections more so, and the mean temperature of this catalytic bed is just high more, thereby its total output is just high more.But, a catalytic bed is divided into many sections more, its cost is just high more, therefore, need seek balance between total output and cost in the industrialization operation.

If the reaction speed of a heat release Catalytic processes raises along with temperature and accelerates (synthetic such as Fischer-Tropsch), so when this technology in the segmentation reactor, one near but do not surmount when carrying out under the temperature that causes temperature runaway, can obtain higher space-time yield.

In addition, this method also can be used for other heat release Catalytic processes, such as synthesis gas system alcohol technology etc.

In above example, only considered in the described model the bigger factor of reaction influence, but, the influence of other factors can be incorporated in this model according to real needs.

In one embodiment, its each formation one of at least two bed sections that one heat release Catalytic processes is configured to catalytic bed is in the interior temperature peak of a predetermined temperature range, and other sections formation temperature peak value not, perhaps the temperature peak of Xing Chenging is not within described predetermined temperature range.

[example six]

Please join table ten, its showed two aspect the CO conversion ratio more near parameter and the result of embodiment 6A and the 6B of commercial scale facility.In embodiment 6A, catalytic bed is loaded the identical catalyst of catalyst that is adopted with above embodiment by traditional approach, the content of synthesis gas is set at 61.5% in the input reaction raw materials, synthesis gas air speed (GHSV) is 138, the maximum temperature that calculates catalytic bed according to described model reaches 249.93 ℃, the CO conversion ratio is 70.71%, and space-time yield is 0.0225mol/ (gcat*h).

In embodiment 6B, catalytic bed is divided into eight isometric bed sections, the identical catalyst of catalyst that is adopted with embodiment 6A that filling is diluted according to the ratio shown in the table ten in these eight bed sections.The content of synthesis gas is set at 100% in the input reaction raw materials, and synthesis gas air speed (GHSV) is 225, calculates as shown in Figure 2 Temperature Distribution according to described model, and the CO conversion ratio is 69.95%, and space-time yield is 0.0363mol/ (gcat*h).As shown in Figure 2, the temperature peak of first to the 7th section is approximately 249.93 ℃, because the consumption of synthesis gas causes the temperature peak of the 8th section to be lower than 249.93 ℃, though the temperature peak of the 8th section is lower, but the space-time yield of this catalytic bed has still promoted 61.6% than the conventional catalyst bed, and its advantage is very remarkable.

Table ten

[example seven]

Example seven has disclosed a traditional reactor and one by embodiment 7A and 7B

The type reactor is respectively applied for Fischer-Tropsch when synthetic, the difference DELTA T and the catalyst of the content of synthesis gas, synthesis gas air speed (GHSV), reactor inlet and tube wall temperature and inside reactor maximum temperature are all identical in reactor pressure, reaction raw materials, but the Different Results that obtains under the different situation of reactor inlet and tube wall temperature temperature.The parameter of embodiment 7A and 7B and result are shown in following table 11.

Table ten one

In embodiment 7A, catalytic bed is pressed evenly filling one catalyst of traditional approach, reactor pressure is 3.1MPa, the content of synthesis gas is 35% in the input reaction raw materials, synthesis gas air speed (GHSV) is 435, reactor inlet and tube wall temperature are 185 ℃, the inside reactor maximum temperature is 200 ℃, the difference DELTA T of reactor inlet and tube wall temperature and inside reactor maximum temperature is 15 ℃, calculate Temperature Distribution shown in curve 7A among Figure 11 according to described model, the CO conversion ratio is 84%, and space-time yield is 0.0725mol/ (gcat*h).

In embodiment 7B, catalytic bed is divided into three isometric bed sections, in each section respectively filling dilution by a certain percentage with embodiment 7A in identical catalyst, the dilution ratio of catalyst is shown in table ten one in three bed sections.Reactor pressure is 3.1MPa among the embodiment 7B, the content of synthesis gas is set at 35% in the input reaction raw materials, synthesis gas air speed (GHSV) is 435, reactor inlet and tube wall temperature are 205 ℃, the inside reactor maximum temperature is 220 ℃, the difference DELTA T of reactor inlet and tube wall temperature and inside reactor maximum temperature is 15 ℃, calculate Temperature Distribution shown in curve 7B among Figure 11 according to described model, the CO conversion ratio is 91%, promoted 8.33% than the conventional catalyst bed, space-time yield is 0.0790mol/ (gcat*h), has promoted 8.97% than the conventional catalyst bed.

Parameter and result by comparing embodiment 7A and embodiment 7B can find, under reactor inlet and the tube wall temperature situation identical with the difference DELTA T of inside reactor maximum temperature, described in the embodiment 7B

The type reactor can improve its conversion per pass and space-time yield by improving reactor inlet and tube wall temperature.

[example eight]

Example eight has disclosed a traditional reactor and one by embodiment 8A and 8B

The type reactor is respectively applied for Fischer-Tropsch when synthetic, difference DELTA T and catalyst in reactor pressure, synthesis gas air speed (GHSV), reactor inlet and tube wall temperature, reactor inlet and tube wall temperature and inside reactor maximum temperature are all identical, but the Different Results that obtains under the different situation of the content of synthesis gas in the reaction raw materials.The parameter of embodiment 8A and 8B and result are shown in following table 12.

Table ten two

In embodiment 8A, catalytic bed is pressed evenly filling one catalyst of traditional approach, reactor pressure is 3.1MPa, the content of synthesis gas is 35% in the input reaction raw materials, synthesis gas air speed (GHSV) is 435, reactor inlet and tube wall temperature are 185 ℃, the inside reactor maximum temperature is 200 ℃, the difference DELTA T of reactor inlet and tube wall temperature and inside reactor maximum temperature is 15 ℃, calculate Temperature Distribution shown in curve 8A among Figure 12 according to described model, the CO conversion ratio is 83%, and space-time yield is 0.070mol/ (gcat*h).

In embodiment 8B, catalytic bed is divided into three isometric bed sections, in each section respectively filling dilution by a certain percentage with embodiment 8A in identical catalyst, the dilution ratio of catalyst is shown in table ten two in three bed sections.Reactor pressure is 3.1MPa among the embodiment 8B, the content of synthesis gas is set at 80% in the input reaction raw materials, synthesis gas air speed (GHSV) is 435, reactor inlet and tube wall temperature are 185 ℃, the inside reactor maximum temperature is 200 ℃, the difference DELTA T of reactor inlet and tube wall temperature and inside reactor maximum temperature is 15 ℃, calculate Temperature Distribution shown in curve 8B among Figure 12 according to described model, the CO conversion ratio is 91%, promoted 9.64% than the conventional catalyst bed, space-time yield is 0.170mol/ (gcat*h), has promoted 143% than the conventional catalyst bed.

Parameter and result by comparing embodiment 8A and embodiment 8B can find, under reactor inlet and the tube wall temperature situation identical with the difference DELTA T of inside reactor maximum temperature, described in the embodiment 8B

The type reactor can improve its conversion per pass and space-time yield by the content that improves synthesis gas in the reaction raw materials.

[example nine]

Example nine has disclosed a traditional reactor and one by embodiment 9A and 9B

The type reactor is respectively applied for Fischer-Tropsch when synthetic, the difference DELTA T of the content of synthesis gas, synthesis gas air speed (GHSV), reactor inlet and tube wall temperature and reactor inlet and tube wall temperature and inside reactor maximum temperature is identical in reactor pressure, reaction raw materials, but the Different Results that obtains under the different situation of catalyst system therefor.The parameter of embodiment 9A and 9B and result are shown in following table 13.

Table ten three

In embodiment 9A, catalytic bed is pressed evenly filling one catalyst of traditional approach, reactor pressure is 3.1MPa, the content of synthesis gas is 35% in the input reaction raw materials, synthesis gas air speed (GHSV) is 435, reactor inlet and tube wall temperature are 185 ℃, the inside reactor maximum temperature is 200 ℃, the difference DELTA T of reactor inlet and tube wall temperature and inside reactor maximum temperature is 15 ℃, calculate Temperature Distribution shown in curve 9A among Figure 13 according to described model, the CO conversion ratio is 84%, and space-time yield is 0.072mol/ (gcat*h).

In embodiment 9B, catalytic bed is divided into three isometric bed sections, the filling another kind of catalyst of dilution by a certain percentage respectively in each section, this activity of such catalysts is 2 times of catalyst among the embodiment 9A, the dilution ratio of catalyst is shown in table ten three in three bed sections.Reactor pressure is 3.1MPa among the embodiment 9B, the content of synthesis gas is set at 35% in the input reaction raw materials, synthesis gas air speed (GHSV) is 435, reactor inlet and tube wall temperature are 185 ℃, the inside reactor maximum temperature is 200 ℃, the difference DELTA T of reactor inlet and tube wall temperature and inside reactor maximum temperature is 15 ℃, calculate Temperature Distribution shown in curve 9B among Figure 13 according to described model, the CO conversion ratio is 90%, promoted 7.14% than the conventional catalyst bed, space-time yield is 0.178mol/ (gcat*h), has promoted 8.33% than the conventional catalyst bed.

Parameter and result by comparing embodiment 9A and embodiment 9B can find, under reactor inlet and the tube wall temperature situation identical with the difference DELTA T of inside reactor maximum temperature, described in the embodiment 9B

The type reactor can improve its conversion per pass and space-time yield by improving activity of such catalysts.

From above-mentioned a plurality of embodiment as can be seen, implementing exothermic catalytic reaction with traditional fixed bed reactors, during such as Fischer-Tropsch synthesis, because emerging of focus, often need the limited reactions temperature, reactant concentration in the restriction raw material, or the activity of limiting catalyst is avoided focus generation temperature runaway.But the limited reactions temperature can reduce the efficient of whole conversion ratio and reactor, reactant concentration in the restriction raw material can increase recycle ratio and corresponding cost, the activity of limiting catalyst then needs the volume of augmenting response equipment, and these all are unfavorable for improving the economic benefit of exothermic catalytic reaction.And disclosed in this application

In the type reactor, by the distribution of catalytic activity in the catalytic bed is set, can distribute in a plurality of focuses of each section of catalytic bed, therefore can or adopt more highly active catalyst to improve the efficient of exothermic catalytic reaction device by concentration of reactants in raising reaction temperature, the increase raw material, thereby increase economic efficiency.

The type reactor is by being provided with a plurality of catalytic bed sections in reaction tube, and controls the catalytic activity of the catalysis material that each section loads, the decline that can slowed down reaction speed causes with reactant consumption.Such as, flow to along reactant by the catalytic activity that makes the catalysis material that each section loads and to increase progressively, the decline that flows to along reactant of slowed down reaction speed widely.

If the catalytic activity of the catalyst only by regulating each section still can't be slowed down the decline of the reaction speed of some or several sections most effectively, can also control reaction speed by the conditioned reaction temperature, so that further improve conversion ratio.Such as, from Temperature Distribution as shown in Figure 2 as can be seen, the decline of the reaction rate of its 8th section does not obtain the most effective slowing down, therefore, can also further slow down the decline of the 8th section reaction speed by the temperature (such as the temperature that improves the 8th section) of regulating each section, farthest to improve whole conversion ratio.

[example ten]

The application's another embodiment provides a kind of heat release Catalytic processes that is used for

The type reaction system, this reaction system comprises the reactor of two or more series connection, and have at least one can with previous embodiment in identical or similar

The type reactor.Please join Figure 11, reaction system 700 comprises one first reactor 710, one second reactor 730 is connected with first reactor 710, one first product gathering-device 721 is used for collecting the portion of product of first reactor, 710 output material streams, one second product gathering-device 723 is used for collecting the portion of product of second reactor, 730 output material streams, and an exhaust gas processing device 725 is used to handle tail gas.First reactor 710 comprises first reaction tube 711, and one first heat-exchange device (or temperature control equipment) 713, the temperature that is used to control first reaction tube, 711 external temperatures and then controls the heat release Catalytic processes that carries out in first reaction tube 711.First reaction tube 711 is provided with a first input end mouth 715 and is used for reactant is imported first reaction tube 711, and one first output port 717 is used for product and residual reactant are derived first reaction tube 711.Also be provided with one first catalytic bed 719 in first reaction tube and be used to load catalysis material, wherein, first catalytic bed 719 is provided with a plurality of first section B1, B2...Bn, and the catalysis material that these first section loaded is arranged so that by a pre-defined rule Temperature Distribution of first catalytic bed 719 roughly meets one first preassigned when first reactor 710 is used to implement the heat release Catalytic processes.The setting of first catalytic bed 719 can be with reference to the optimization method among the above embodiment.

When 710 of first reactors were provided with one first reaction tube 711, the first input end mouth of first reaction tube 711 and the input port of first reactor 710 can be same port.In like manner, first output port 717 also is like this.

In one embodiment, first preassigned is that the maximum temperature of first section of first predetermined quantity equals one first predetermined temperature or is positioned at one first predetermined temperature range, and wherein, first predetermined quantity is more than or equal to two.

In another embodiment, first preassigned is that the maximum temperature of preassigned at least two first sections equals first predetermined temperature or is positioned at first predetermined temperature range.

In a preferred embodiment, the catalytic activity of the catalysis material that each first section is loaded is configured to when implementing the heat release Catalytic processes in first reactor 710, and the maximum temperature of each first section equals first predetermined temperature or is positioned at first predetermined temperature range.

Second reactor 730 comprises second reaction tube 731, and one second heat-exchange device (or temperature control equipment) 733, the temperature that is used to control second reaction tube, 731 external temperatures and then controls the heat release Catalytic processes that carries out in second reaction tube 731.Second reaction tube 731 is provided with one second input port 735 and is used for reactant is imported second reaction tube 731, and one second output port 737 is used for product and residual reactant are derived second reaction tube 731.Also be provided with one second catalytic bed 739 in second reaction tube 731 and be used to load catalysis material.In one embodiment, second catalytic bed 739 is provided with a plurality of second section D1, D2...Dn, and the catalytic activity of the catalysis material that these second section loaded is configured to when implementing the heat release Catalytic processes in second reactor 730, and the Temperature Distribution of second catalytic bed 739 meets one second preassigned.

In one embodiment, the catalysis material that second catalytic bed, 739 each second section are loaded is identical, and second preassigned can be that the maximum temperature of second catalytic bed 739 equals one second predetermined temperature or is positioned at one second predetermined temperature range.

In another embodiment, second preassigned is that the maximum temperature of second section of second predetermined quantity equals second predetermined temperature or is positioned at second predetermined temperature range, and wherein, second predetermined quantity is more than or equal to two.

In another embodiment, second preassigned is that the maximum temperature of preassigned at least two second sections equals second predetermined temperature or is positioned at second predetermined temperature range.

In a preferred embodiment, the catalytic activity of the catalysis material that each second section is loaded is configured to when implementing the heat release Catalytic processes in second reactor 730, and the maximum temperature of each second section equals second predetermined temperature or is positioned at second predetermined temperature range.

For Fischer-Tropsch was synthetic, predetermined temperature can be the maximum temperature (critical-temperature) that is allowed under the prerequisite that temperature runaway or catalyst burn not taking place.In practical operation, to consider based on safety, a certain temperature that can choose subcritical temperature certain amplitude is as predetermined temperature.For high temperature fischer-tropsch was synthetic, predetermined temperature was generally 300 ℃～350 ℃; For the low temperature Fischer-Tropsch was synthetic, predetermined temperature was generally 200 ℃～240 ℃.Predetermined temperature range can be 20 ℃ scope below predetermined temperature, and is preferred, can be 10 ℃ scope below predetermined temperature, preferred, can be 5 ℃ scope below predetermined temperature.

At one more preferably among the embodiment, the catalytic activity that first catalytic bed 719 flows to the catalysis material that first section in downstream load along reactant is higher than first catalysis material that section is loaded of upstream; The catalytic activity that second catalytic bed 739 flows to the catalysis material that second section in downstream load along reactant is higher than second catalysis material that section is loaded of upstream.

In one embodiment, first catalytic bed, 719 each first section are loaded first catalyst, and dilute to reach the different purpose of catalytic activity with first diluent.Second catalytic bed, 739 each second section are loaded second catalyst, and dilute to reach the different purpose of catalytic activity with second diluent.In one embodiment, first catalyst and second catalyst are catalyst of the same race.In another embodiment, first catalyst and second catalyst are different catalysts, such as, first catalyst is applicable to lower reaction temperature, and second catalyst is applicable to higher reaction temperature, is applicable to the leading portion reaction such as, first catalyst again, and second catalyst is applicable to the back segment reaction, and the product that leading portion is reacted further is converted into target product.

In another embodiment, first reactor 710 can be provided with a plurality of first reaction tube, 711, the second reactors 730 can be provided with a plurality of second reaction tube 731, i.e. calandria type fixed bed reactors.

Please join Figure 11 again, the first product gathering-device 721 is located between first output port 717 and second input port 735, is used to collect the liquid product of first reaction tube, 711 outputs, such as wax and water.Wherein, the collection of liquid product can realize by condensation.The synthetic water byproduct of Fischer-Tropsch can produce harmful effect to cobalt-base catalyst, therefore, adopts at second reactor under the situation of cobalt-base catalyst, and the water of removing in the product is favourable for second reactor.

The second product gathering-device 723 is connected with second output port 737, is used to collect the liquid product of second reaction tube, 731 outputs.Exhaust gas processing device 725 is connected with the second product gathering-device 723, is used to handle tail gas.In one embodiment, exhaust gas processing device 725 comprises an exhaust combustion device (not shown), is used for combustion tail gas and generates electricity.

Synthesize example with Fischer-Tropsch, according to the analysis of example one to example six, the setting of first reactor 710 has significantly improved the conversion ratio of synthesis gas than the pre-existing reactors setting, that is to say, under the situation that does not have second reactor 730 to participate in, significantly promoted the effective rate of utilization of synthesis gas than prior art.Because the conversion ratio of first reactor 710 is higher, the content of importing synthesis gas in the material stream of second reaction tube 731 is lower, this makes the heat release of under same reaction conditions second reaction tube 731 much smaller than first reaction tube 711, the temperature that is to say second catalytic bed 739 does not far reach critical-temperature, thereby is underutilized.In one embodiment, the external temperature of second reaction tube 731 is arranged to be higher than the external temperature of first reaction tube 711, thereby the temperature that makes second catalytic bed 739 near critical-temperature to improve the conversion ratio of second reactor 730, further reduce the content of synthesis gas in the tail gas, finally significantly improve the effective rate of utilization of synthesis gas.

In one embodiment, can the reactor of right quantity be set according to real needs and situation.Please join Figure 12, reactor 750,760 and 770 series connection, the external temperature of the reaction tube of reactor 750 is T1 ', and the external temperature of the reaction tube of reactor 760 is T2 ', and the external temperature of the reaction tube of reactor 770 is T3 '.Wherein, T3 '＞T2 '＞T1 '.

In another embodiment, because it is lower to export the content of synthesis gas in the material stream of first reactor 710, a plurality of first parallel reactors can be connected with one second reactor, to improve the utilization rate of second reactor.

The application's another embodiment provides a kind of method 810 that designs the heat release Catalytic processes.Please join Figure 13, method 810 may further comprise the steps: the catalysis material that loads according to each first section of first catalytic bed 719 and the reaction condition of first reactor 710 obtain the Temperature Distribution (step 811) of first catalytic bed 719; The Temperature Distribution of first catalytic bed 719 that step 811 is obtained and one first predetermined temperature or one first predetermined temperature range compare (step 813); Whether the Temperature Distribution that judges whether first catalytic bed 719 meets one first preassigned (step 815); If the judged result of step 815 is a "No", then adjust catalysis material that corresponding first section of first catalytic bed 719 load or/and the reaction condition (step 817) of first reactor 710, and repeating step 811 to 815 is until the combination of the reaction condition of the configuration of the catalysis material of first catalytic bed, 719 fillings of the Temperature Distribution that obtains to produce first catalytic bed 719 that meets first preassigned and first reactor 710; If the judged result of step 815 is a "Yes", obtains the flow that flows by first catalytic bed, 719 materials output and that import second catalytic bed 739 and form (step 819); The flow of catalysis material, the reaction condition of second reactor 730 and the material stream that step 819 obtains that loads according to each second section of second catalytic bed 739 and form the Temperature Distribution (step 821) that obtains second catalytic bed 739; The Temperature Distribution of second catalytic bed 739 that step 821 is obtained and one second predetermined temperature or one second predetermined temperature range compare (step 823); Whether the Temperature Distribution of judging second catalytic bed 739 meets one second preassigned (step 825); If the judged result of step 825 is a "No", then adjust catalysis material that corresponding second section of second catalytic bed 739 load or/and the external temperature (step 827) of second reaction tube 731, and repeating step 821 to 825 is until the combination of the external temperature of the reaction condition of the configuration of the catalysis material of second catalytic bed, 739 fillings of the Temperature Distribution that obtains to produce second catalytic bed 739 that meets second standard, second reactor 730 and second reaction tube 731; If the judged result of step 825 is a "Yes", obtain the combination (step 829) of the external temperature of the reaction condition of configuration, second reactor 730 of catalysis material of reaction condition, 739 fillings of second catalytic bed of configuration, first reactor 710 of the catalysis material of first catalytic bed, 719 fillings and second reaction tube 731.

As previously mentioned, some or all steps that method is 810 kinds can be implemented by computer simulation, also can implement by experiment.

In one embodiment, the adjustment of step 817 pair reaction condition can be the adjustment to the reaction raw materials flow, also can be the adjustment that reaction raw materials is formed.

In one embodiment, step 819 can be to collect situation (such as temperature, pressure etc.) according to the configuration of the catalysis material of the reaction condition of first reactor 710, the filling of first catalytic bed and the product of the first product gathering-device 721, obtains the flow and the composition of the material stream of input second reactor 730.

In one embodiment, first predetermined temperature can equal second predetermined temperature, and first predetermined temperature range can equal second predetermined temperature range.

Wherein, the method for above-mentioned design heat release Catalytic processes can realize by computer simulation, also can realize by actual experiment.Three embodiment that below will be by computer simulation (routine I, J, K) advantage of the scheme that present patent application is described is provided.

Following table 14 has been listed routine I, J, the common parameters such as reaction condition that adopt of K.

Table ten four

Reactor inside diameter (cm)	??1.07	Specific heat capacity (J/gK)
				Catalyst granules diameter (mm)	??0.25	??CO	??1.07
Diluent size (mm)	??0.25	??H 2	??14.5
				Temperature (℃)	??185/193	??H 2O	??2.80
Pressure (atm)	??31	??CH 4	??6.16
				Air speed (GHSV)	??1105	Reaction heat Δ H (kJ/mol)	??160
Catalyst apparent density (g/ml)	??1.10	Effective diffusivity (cm 2/s)
				Catalytic bed height (cm)	??30/10	??CO	??10 -6
??H 2/CO	??1.9	??H 2	??10 -5
				Heat exchange coefficient (J/scm 2·K)	??0.02	??H 2O	??10 -6
Thermal conductivity (J/scmK)	??0.1	??CH 4	??10 -6

Following table 15 has been listed routine I, J, the K distribution of catalytic bed active factors, reaction condition and reaction result separately.

Table ten five

In one embodiment, routine I, J, the catalytic bed temperature among the K distributes and conversion ratio is based on following table 16 listed reaction rate law calculation of parameter gained.

Table ten six

Reaction	??k 0_H 2(1/h)	??E a_H 2(kJ/mol)
			?C 2+Hydro carbons is synthetic	??1.30E+11	??102
Methane is synthetic	??2.16E+13	??112

Please join Figure 17, curve i, j, k are respectively routine I, J, the catalytic bed temperature distribution curve of K.Because routine J is identical with the active factors distribution and the reaction condition of first catalytic bed among the routine K, so the temperature distribution history of both first catalytic beds overlaps.Example I, J, among the K, the first catalytic bed length overall 30cm is divided into three first sections equably, and the second catalytic bed length overall 10cm is divided into three second sections equably.

Among the example I, first catalytic bed and second catalytic bed are all loaded undiluted catalyst, and therefore, the active factors of first catalytic bed was distributed as 1: 1: 1, and the active factors of second catalytic bed was distributed as 1: 1: 1.The content of synthesis gas is 65% in input gas, when the external temperature of first reaction tube is set to 185 ℃, the maximum temperature of first catalytic bed in first first section that flows to along reactant forms and reaches about 201 ℃ (being set to the maximum temperature of permission in the present embodiment), the external temperature of second reaction tube is set at 193 ℃, the maximum temperature of second catalytic bed in first second section that flows to along reactant forms and reaches about 200 ℃, at this moment, its carbon monoxide conversion ratio is 76%.

Among the example J, first catalytic bed is loaded diluted catalyst respectively along first and second first section that reactant flows to, and the 3rd first section loaded undiluted catalyst, and its active factors was distributed as 0.69: 0.8: 1.Second catalytic bed is loaded diluted catalyst respectively along first and second second section that reactant flows to, and the 3rd second section loaded undiluted catalyst, and its active factors was distributed as 0.69: 0.8: 1.The content of synthesis gas is 90% in input gas, when the external temperature of first reaction tube is set to 185 ℃, the maximum temperature of three first sections is between 199-201 ℃, the external temperature of second reaction tube is set at 193 ℃, the maximum temperature of three second sections is between 199-201 ℃, at this moment, its carbon monoxide conversion ratio is 79%.

Among the example K, first catalytic bed is loaded diluted catalyst respectively along first and second first section that reactant flows to, and the 3rd first section loaded undiluted catalyst, and its active factors was distributed as 0.69: 0.8: 1.Second catalytic bed is loaded undiluted catalyst.The content of synthesis gas is 90% in input gas, when the external temperature of first reaction tube is set to 185 ℃, the maximum temperature of three first sections is between 199-201 ℃, the external temperature of second reaction tube is set at 190.5 ℃, the maximum temperature of second catalytic bed forms in first second section that flows to along reactant and is about 201 ℃, at this moment, its carbon monoxide conversion ratio is 79%.

Please join table ten two, the more routine I of the space-time yield of routine J and routine K (representing space-time yield with the content of synthesis gas and the product of synthesis gas conversion ratio in the input gas) has all improved 44%.

Please join Figure 18, another embodiment of the application provides a kind of method 830 of enforcement one heat release Catalytic processes, it may further comprise the steps: form one first catalytic bed in one first reaction tube of one first reactor, first catalytic bed comprises a plurality of first section (step 831); Form one second catalytic bed in one second reaction tube of one second reactor, second reactor is connected with described first reactor, so that the material stream of small part first reactor output is as reaction raw materials (step 833); In described first reactor and second reactor, implement described heat release Catalytic processes, make the Temperature Distribution of first catalytic bed meet first a predetermined temperature conditions, make the Temperature Distribution of second catalytic bed meet second a predetermined temperature conditions (step 835).

In one embodiment, first temperature conditions can be that the maximum temperature of first section of first quantity of being scheduled to equals first a predetermined temperature or is positioned at first a predetermined temperature range, and wherein, first quantity is more than or equal to two; First temperature conditions also can be that the maximum temperature of preassigned at least two first sections equals first temperature or is positioned at first temperature range; First temperature conditions can also be that the maximum temperature of at least two first sections equals first temperature or is within first temperature range.

In one embodiment, second temperature conditions is that the maximum temperature of second catalytic bed equals second a predetermined temperature or is positioned at second a predetermined temperature range.

In one embodiment, second catalytic bed comprises a plurality of second section that is filled with catalysis material, second temperature conditions is that the maximum temperature of second section of predetermined second quantity equals second a predetermined temperature or is in the second predetermined temperature range, wherein, second quantity is more than or equal to two; Second temperature conditions also can be that the maximum temperature of preassigned at least two second sections equals second temperature or is in second temperature range.

Institute is known as industry, and many kinds of catalyst can be used for Fischer-Tropsch and synthesize.Fischer-tropsch synthetic catalyst can be the active component that is carried on carrier, also can be the active component that is not carried on carrier.Carrier is generally porous material, for active component provides mechanical support, such as boehmite (boehmite), refractory oxide (as silica, aluminium oxide, titanium oxide, thorium oxide, zirconia etc., or its mixture), aluminum fluoride etc.Active component can be the 8th in the periodic table of elements, the 9th and the tenth family's metal, more preferably, can be iron, cobalt, nickel, ruthenium or its combination.Further, fischer-tropsch synthetic catalyst can also comprise one or more auxiliary agents, auxiliary agent can be first family metal, second family metal, three-group metal, the 4th family's metal, the 5th family's metal, seven races' metal, the 8th family's metal, nine degrees of kindred's metal, the tenth family's metal, the tenth gang's metal and the tenth three-group metal, comprises noble metal and boron.Usually, during as catalyst, these metals are in goes back ortho states (such as metallic state).

Claims (34)

1. reactor that is used for a heat release Catalytic processes comprises:

Reaction tube; And

Be located in the described reaction tube and flow to the catalytic bed of extending along reactant, it is characterized in that, this catalytic bed flows to along reactant and is provided with a plurality of sections, these a plurality of sections are configured to when implementing described heat release Catalytic processes in this reactor, make the maximum temperature of at least two bed sections its each equal predetermined first temperature or are within predetermined first temperature range.

2. reactor as claimed in claim 1 is characterized in that: the catalytic activity that reactant flows to the catalysis material that the bed section in downstream loaded is higher than the catalytic activity of the catalysis material that the bed section of upstream loaded.

3. reactor as claimed in claim 2 is characterized in that: the catalysis material that described a plurality of sections are loaded can comprise diluent, the content difference of diluent in the catalysis material that each section is loaded, thus make the catalytic activity difference of each section.

4. reactor as claimed in claim 1 is characterized in that: described heat release Catalytic processes is implemented under a predetermined reaction condition configuration, and described a plurality of sections are based on that this predetermined reaction condition configuration is provided with.

5. reactor as claimed in claim 4 is characterized in that: described predetermined reaction condition configuration comprises the reactant air speed.

6. reactor as claimed in claim 1 is characterized in that: described heat release Catalytic processes is a fischer-tropsch synthesis process.

7. reactor as claimed in claim 1 is characterized in that: the peak temperature of described maximum temperature for forming in corresponding bed section.

8. method of implementing a heat release Catalytic processes comprises:

Form a catalytic bed in a reaction tube, this catalytic bed comprises a plurality of sections; And

In described reaction tube, implement described heat release Catalytic processes, make the maximum temperature of at least two bed sections its each equal a predetermined temperature or be positioned within the preset range.

9. method as claimed in claim 8 is characterized in that: the step that forms catalytic bed also comprises a regulating step, and the catalytic activity of regulating the catalysis material that fills in each section is or/and reaction condition.

10. method as claimed in claim 9 is characterized in that, described regulating step also comprises:

The acquisition catalytic bed temperature distributes;

Described Temperature Distribution and a predetermined temperature or a predetermined temperature range are compared; And

The catalytic activity of catalysis material of regulating corresponding bed section according to the result of described comparison is or/and reaction condition.

11. a computer readable medium stores and can be made this processor implement to be provided with the instruction of the method for a heat release Catalytic processes after being carried out by computer processor, this method comprises:

Receive a catalytic bed setting and a reaction condition setting, this catalytic bed setting comprises the bed hop count amount of this catalytic bed and the catalytic activity of the catalysis material that each section is loaded, wherein, this catalytic bed is to be located in the reaction tube, and described reaction condition setting comprises the reactant air speed;

According to described catalytic bed setting and described reaction condition the distribution of calculating acquisition one catalytic bed temperature is set;

Described catalytic bed temperature distribution and first temperature of being scheduled to or first temperature range of being scheduled to are compared to judge whether it meets first a predetermined temperature standard;

If distributing, described catalytic bed temperature do not meet described first temperature standard, then relatively regulate described catalytic bed setting or/and the reaction condition setting, and the above step of repetition is set until the catalytic bed temperature distribution that obtains to meet described first temperature standard according to catalytic bed setting after regulating and reaction condition according to described.

12. method as claimed in claim 11 is characterized in that, described first temperature standard can for following one of arbitrarily: the maximum temperature of previously selected at least two bed sections equals described first temperature; Or the maximum temperature of previously selected at least two bed sections is within described first temperature range; Or maximum temperature equals the quantity of bed section of described first temperature greater than a predetermined quantity; Or maximum temperature is in the quantity of the bed section in described first temperature range greater than a predetermined quantity.

13. method as claimed in claim 11 is characterized in that, described reaction condition setting comprises the reactant air speed.

14. method as claimed in claim 13 is characterized in that, described reaction condition setting comprises the reaction tube wall temperature.

15. reactor assembly that is used for the heat release Catalytic processes, comprise first reactor and second reactor, wherein, second reactor is connected with first reactor and is made product and residual reactant to the output of small part first reactor can be imported into second reactor, it is characterized in that: described first and second reactors comprise first and second reaction tubes and first and second heat-exchange devices respectively, and the external temperature that is respectively applied for first and second reaction tubes is controlled at T ₁And T ₂, wherein, T ₂Be higher than T ₁

Wherein, be respectively equipped with first and second catalytic beds in described first and second reaction tubes, described first catalytic bed flows to along reactant and is provided with a plurality of first section, make the reaction compartment in this first reaction tube be divided into a plurality of first conversion zones, the catalysis material that these first section loaded makes when this reactor assembly is used to implement described heat release Catalytic processes, has at least the maximum temperature of two first conversion zones to equal first a predetermined temperature in described a plurality of first conversion zones or is within the first predetermined temperature range.

16. reactor assembly as claimed in claim 15 is characterized in that: the catalytic activity of the catalysis material that first section of corresponding described at least two first conversion zones loaded is different.

17. reactor assembly as claimed in claim 16, it is characterized in that: in first section of corresponding described at least two first conversion zones, the catalytic activity that flows to the catalysis material that first section in downstream load along reactant is higher than the catalytic activity of the catalysis material that first section of upstream load.

18. reactor assembly as claimed in claim 16, it is characterized in that: the catalysis material that described a plurality of first section are loaded can comprise diluent, the content difference of diluent in the catalysis material that each first section is loaded, thus make the respectively catalytic activity difference of first section.

19. reactor assembly as claimed in claim 15, it is characterized in that: described second catalytic bed flows to along reactant and is provided with a plurality of second section, and make the reaction compartment in this second reaction tube be divided into a plurality of second conversion zones, described a plurality of second conversion zones have at least the maximum temperature of two second conversion zones to load because of described a plurality of second section when this reactor assembly is used for implementing described heat release Catalytic processes catalysis material and described T ₂And equal second a predetermined temperature or be within the second predetermined temperature range.

20. reactor assembly as claimed in claim 19 is characterized in that: the catalytic activity that flows to the catalysis material that second section in downstream load along reactant is higher than the catalytic activity of the catalysis material that second section of upstream load.

21. reactor assembly as claimed in claim 20, it is characterized in that: the catalysis material that described a plurality of second section are loaded can comprise diluent, the ratio difference of diluent in the catalysis material that each second section is loaded, thus make the respectively catalytic activity difference of second section.

22. reactor assembly as claimed in claim 15 is characterized in that: described heat release Catalytic processes is a fischer-tropsch synthesis process.

23. reactor assembly as claimed in claim 15 is characterized in that: the peak temperature of the maximum temperature of described first conversion zone in first conversion zone of correspondence, forming.

24. reactor assembly as claimed in claim 19 is characterized in that: the peak temperature of the maximum temperature of described second conversion zone in second conversion zone of correspondence, forming.

25. reactor assembly as claimed in claim 15 is characterized in that: between first reactor and second reactor, be provided with one first product gathering-device, collect the liquid product of part by the output of first reaction tube.

26. a method that designs the heat release Catalytic processes may further comprise the steps:

Initial setting first reactor and corresponding reaction condition,

Initial setting second reactor and corresponding reaction condition, described second reactor is connected with first reactor, make the material stream of exporting to small part first reactor be transfused to the reaction raw materials of second reactor as second reactor, described first and second reactors comprise first and second reaction tubes respectively and are located at the first and second interior catalytic beds of first and second reaction tubes respectively that described first catalytic bed comprises a plurality of first section that is filled with catalysis material;

The catalysis material that loads according to each first section and the reaction condition of first reactor obtain the Temperature Distribution of first catalytic bed;

If the Temperature Distribution of first catalytic bed that is obtained is inconsistent the first predetermined temperature conditions of unification, adjust catalysis material that first section load or/and the reaction condition of first reactor;

If the Temperature Distribution of first catalytic bed that is obtained symbol and the described first predetermined temperature conditions obtain the flow that the material by the output of first reactor flows and form;

According to obtained by the flow of the material stream of first reactor output and form, catalysis material that second catalytic bed is loaded and the reaction condition of second reactor, obtain the Temperature Distribution of second catalytic bed;

If the Temperature Distribution of second catalytic bed that is obtained is inconsistent the second predetermined temperature conditions of unification, adjust catalysis material that second section load or/and the reaction condition of second reactor.

27. method as claimed in claim 26, it is characterized in that: first temperature conditions can equal first a predetermined temperature or be positioned at first a predetermined temperature range for the maximum temperature of first section of predetermined first quantity, wherein, first quantity is more than or equal to two; First temperature conditions also can equal first temperature at least or be positioned at first temperature range for the maximum temperature of preassigned two first sections; First temperature conditions can also equal first temperature at least or be within first temperature range for the maximum temperature of two first sections.

28. method as claimed in claim 26 is characterized in that: the maximum temperature that described second temperature conditions is second catalytic bed equals second a predetermined temperature or is positioned at second a predetermined temperature range.

29. method as claimed in claim 26, it is characterized in that: described second catalytic bed comprises a plurality of second section that is filled with catalysis material, described second temperature conditions is that the maximum temperature of second section of predetermined second quantity equals second a predetermined temperature or is in the second predetermined temperature range, wherein, second quantity is more than or equal to two; Second temperature conditions also can equal second temperature at least or be in second temperature range for the maximum temperature of preassigned two second sections.

30. method as claimed in claim 26 is characterized in that: the reaction condition of adjusting second reactor comprises the external temperature of adjusting second reaction tube.

31. a method of implementing a heat release Catalytic processes may further comprise the steps:

Form one first catalytic bed in one first reaction tube of one first reactor, first catalytic bed comprises a plurality of first section;

Form one second catalytic bed in one second reaction tube of one second reactor, second reactor is connected with described first reactor, so that the material stream of small part first reactor output is as reaction raw materials;

Be higher than under the condition of the first reaction tube external temperature at the second reaction tube external temperature, in described first reactor and second reactor, implement described heat release Catalytic processes, make the Temperature Distribution of first catalytic bed meet first a predetermined temperature conditions, make the Temperature Distribution of second catalytic bed meet second a predetermined temperature conditions.

32. method as claimed in claim 31, it is characterized in that, first temperature conditions can be following one of arbitrarily: the maximum temperature of first section of predetermined first quantity equals first a predetermined temperature or is positioned at first a predetermined temperature range, wherein, first quantity is more than or equal to two; The maximum temperature of preassigned at least two first sections equals first temperature or is positioned at first temperature range; The maximum temperature of at least two first sections equals first temperature or is within first temperature range.

33. method as claimed in claim 31 is characterized in that: the maximum temperature that described second temperature conditions is second catalytic bed equals second a predetermined temperature or is positioned at second a predetermined temperature range.

34. method as claimed in claim 31, it is characterized in that: described second catalytic bed comprises a plurality of second section that is filled with catalysis material, described second temperature conditions is that the maximum temperature of second section of predetermined second quantity equals second a predetermined temperature or is in the second predetermined temperature range, wherein, second quantity is more than or equal to two; Second temperature conditions also can be that the maximum temperature of preassigned at least two second sections equals second temperature or is in second temperature range.

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