CN101468303A - Device for developing catalysis technique - Google Patents

Abstract

The invention relates to a catalytic process development device. The device comprises a lab-scale composite multistage plug flow reactor which consists of at least three tandem plug flow reactors in which a catalyst bed layer consisting of crushed or industrial-specification catalyst granules can be loaded. Dynamics, mass transfer and thermal transfer performances of the reactors are determined through sampling and analyzing discharge of the reactors. The device is also provided with a detection reactor which is arranged parallel to the composite multistage reactor to determine influence of additional fresh reactant, reaction products, byproducts or pollutants and toxic substances likely present in industrial reactor raw materials on reaction process. The detection reactor can be a multistage tandem or single-stage plug flow reactor or a continuous stirred tank reactor with the same stage number as the composite multistage plug flow reactor. In addition, the invention also relates to a method for development of the catalytic process. Therefore, the device can speed up the course of industrialization scale.

Description

A kind of development device of Catalytic processes

[technical field]

The present invention relates to a kind of device of catalytic process exploitation, this device can be used for being found to commercial catalyst for application and laminar flow Catalytic processes thereof so that the quick exploitation of lower cost is a kind of at first from it.Especially, the present invention refers in particular to a kind of piston flow reactor device and relates to the method for amplifying (Scale-up) its Catalytic processes fast.

[background technology]

In order to amplify (Scale-up) a kind of laminar flow Catalytic processes, just need the influence of research reaction time (Time onStream), reactant residence time (Residence Time), catalyst particle size, shape and its other features and temperature curve (Temperature Profile) to reaction rate and catalyst selectivity.In the research of traditional amplification, what the first step related to earlier usually is selecting catalyst and some intrinsic propestieses that determine selected catalyst.In order to reduce the influence of matter biography to operating process, the operation of this step often is to select the catalyst or the powder catalyst of the crushing of process dilution to carry out under isothermy.When the operation of this step begins, need test the changeability of reaction process, its main purpose is to determine the influence to reaction rate and catalyst selectivity of air speed, pressure and reactant residence time.Like this, the employed catalyst activity of this step is reached optionally definite six wheat harvesting periods that often need to year.Last in this step operating process still needs the changeability of reaction process is tested again, is used for determining whether above characteristic can change along with the reaction time.

Secondly, select the described catalyst of commercial size in isothermal reactor, to test.The catalyst of so-called commercial size, its catalyst compared to above-mentioned crushing has bigger particle size or has specific shape, is used for reducing the pressure drop in the operating process.Because reactant or product enter or leave the restriction that quality is transmitted in the catalyst hole process in course of reaction, the reaction rate and the selectivity of general large-size particle catalyst are relatively poor.When the beginning and finish of this operating process, also often need study with detecting catalyst activity and selectivity the changeability of technology equally, so just need about year again.In addition, this step often uses laboratory-scale reactors to carry out.

The reactor of the checking scale that is provided with one or more reaction tubes is normally selected in final step for use, the catalyst of the described commercial size of test under the condition of thermal insulation.The about 25.4mm of the internal diameter of described reaction tube (1 inch).In addition, in order better to probe into the influence that heat transmits, described reactor is standing puts 6-8 reaction tube, and the distance between reaction tube is provided with according to the distance that commercial scale adopts.In an exothermic reaction, as in tubular reactor or in the piston flow reactor that does not have special heat extraction equipment, the variation of temperature curve depends on the degree that removes reaction heat continuously.Variation of temperature has remarkable influence to selection of catalysts, reaction rate and activity.In the test of this step, often can measure the trend of reaction generation focus or temperature control.Equally, this step often needs the time more than a year.

As seen, the finishing the normal time of needs more than 3 years of this series of steps, and usually differ and obtain institute surely and be useful on and amplify needed data.For a lot of catalyst, its reaction rate and selectivity are relevant with the time that reactant residence time and reactor continue to react.This relation is the result of catalyst condition or specifications vary, and this result to be the continuous variation that gas or liquid are formed owing to the time of catalyst reaction or from reactor inlet to exit procedure cause.Such as catalyst run into material such as hydrogen sulfide and ammonia and with its reaction in, the water oxidation that catalyst can be formed in the conversion process can form cover layer and catalyst poisoning etc. in its surface, thereby cause catalyst condition or specifications vary.In addition, because surface-catalyzed reactions takes place in reactant and product in catalyst pores and accumulating in the hole also can cause matter to pass the reduction of speed (MassTransfer Rate).

Recently, the high flux experimental technique is used to new catalyst and Catalytic processes thereof are studied.These high flux experimental techniques are generally carried out under the influence that reduces heat biography and matter biography, and it only needs seldom to measure the catalyst of (being less than 2 milliliters) and have very high rates of heat transfer.Yet, this technology, such as United States Patent (USP) the 6th, 149, No. 882 and the 6th, 869, disclosed for No. 799, though can the intrinsic performance of different catalyst to be selected be compared, can not be provided for amplifying needed data.

So the development device that needs a kind of new Catalytic processes is in order to overcome the deficiencies in the prior art.

[summary of the invention]

The object of the present invention is to provide a kind ofly to have the device of lower cost and relate to the method for using this device, this device and method is used to develop and a kind ofly is found to the commercial catalysis flow process of using at first from it.

The method of described use catalytic unit can be tested one or more catalyst with one or more forms simultaneously.

In one embodiment of the invention, described device comprises first by three or more, as 4, and the combined multi-stage piston flow reactor that the reactor of 5 or 6 series connection is formed.The normal beds that is mixed with inertia dilution particle that loads in the reactor, the internal diameter of reactor are 10 times of reduced size in dilution particle or the catalyst granules.In addition, be provided with the sampling valve that links to each other with every stage reactor, be used for the effluent of reactor is carried out sampling analysis.

Under most situation, as in a temperature control equipment, keeping it in a stationary temperature environment by combined multi-stage reactor as described in being provided with.In exothermic reaction, in Fischer-Tropsch synthesis, temperature control equipment can have various ways, as is circulating boiling water or fluidization sand-bath.In the endothermic reaction, in paraffin dehydrogenation or catalytic reforming reaction, temperature control equipment can be the fluidization sand-bath or it is provided with heater, as electric heater, in order to give the heat supply of combined multi-stage reactor so that reactor maintains constant predetermined temperature.

Certainly, also can set different temperature to different reactors as required, at this moment, can utilize heater that certain stage reactor or certain group tandem reactor are heated separately.Like this, be convenient to the dynamics of comparative studies group or certain stage reactor and certain heat and pass factor.

In an embodiment of the present invention, three or more single-stage reactors in the described combined multi-stage reactor can be mounted with the catalyst of same size, so just can simulate the characteristic of an independent composite catalyst bed of forming by the beds that loads in described three or more the single-stage reactors, obtain along described independent composite catalyst bed the related data of the variation of the catalyst performance of its different longitudinal position and reactor performance top rake (lengthwise position).In addition, in an embodiment of the present invention, also can comprise second or more a plurality of similar combined multi-stage tandem reactor, itself and described first combined multi-stage tandem reactor be arranged in parallel.Wherein, in described second or the more a plurality of combined multi-stage tandem reactor one can load crushing or powder catalyst, the one or more catalyst that load the commercial size of one or more shapes or size in the remaining reactor.Like this, just can study that the matter relevant with lengthwise position in the beds of fixed bed reactors passes, heat passes and dynamics.In addition, carry out sampling analysis by effluent to the reactor in the combined multi-stage reactor, just can determine the activity and the selectivity of every stage reactor, and, also can determine the selectivity of every stage reactor and relative reaction rate thereof by this relation because the conversion ratio and the time of staying of every stage reactor have certain relation.

Beds in a combined multi-stage tandem reactor for the crushing or the fine catalyst particle, and when reactor is operated in isothermy, obtain at first reaction rate and optionally data result can be considered to catalyst in the selectivity and the intrinsic reaction rate thereof in when beginning reaction, get rid of promptly that matter passes and heat passes the reaction rate of influence; Subsequently, the carrying out along with reaction just comprised the influence that catalyst ageing brought in the intrinsic reaction rate that obtains.In any case, the macroreaction speed of this moment equals the intrinsic reaction rate, and the efficiency factor that promptly is exactly reaction is 1.In addition, for fresh and aging catalyst, optionally data result can come directly to weigh the essential selectivity of catalyst and the relation of conversion ratio.

Beds in another laboratory scale combined multi-stage series connection piston flow reactor is the catalyst granules of commercial size, it is mounted with multistage reactor crushing or pulverous catalyst granules of the same race parallel reacting under isothermy in identical temperature environment with described, and when all having the reactor of identical progression, thereby determine for the very important efficiency factor relevant of the industrialization of Catalytic processes and other information with lengthwise position by the comparison of two groups of multistage reactor performances.

In addition, by analysis, thereby can obtain the relation data of the apparent reaction rates and the time of staying to the effluent of the combined multi-stage reactor that is mounted with the commercial size catalyst granules under isothermy, operated.Like this, under the known situation of intrinsic reaction rate,, just can directly obtain the relation of efficiency factor and conversion ratio by the relation data of its conversion ratio and the time of staying for catalyst crushing and commercial size.At this moment, the diameter of known efficiency factor, intrinsic reaction rate and full-size catalyst granules (relevant) with the thickness L of beds, thus can determine the relation of the effective diffusivity of full-size catalyst granules by the Thiele modulus with respect to conversion ratio.

The acquisition of these data just can be used to probe into the mechanism that matter passes retardance, as having at the reactor inlet place that lower diffusivity shows since the influence of the initial product of raw material components, reaction maybe in considering fluid during the true dividing potential drop of a certain component, raw material components in the concentration on the catalyst activity position less than the former of expection concentration thereby on catalyst hole or surface, form matter biography resistance.When having lower diffusivity at reactor exit, it shows that product accumulation or effluent fluid and catalyst takes place reacts.When reaction relates to multiple reactant with different diffusivitys, because efficiency factor can be reflected in the variation of component between gaseous material and the catalyst surface, so apparent reaction rates and selectivity are all often relevant with efficiency factor.

At phase reaction, as relate in the process of the hydrocracking of raw material with relative volatility and fixedness and solid catalyst and hydro-conversion, the effect of vapor liquid equilibrium (Vapor-liquid Equilibrium) can have influence on the macrodynamics (Apparent Kinetics) of system.In this case, just can make a difference simultaneously to those, the i.e. reaction that has competition is to each other studied, just as people such as Denayer at " chemical reactor engineering world periodical " (International Journal of Chemical Reactor Engineering), 2003, volume 1, disclose among the paper A36 respectively under 4.5bar and 100bar pressure to the mixture of different material, as mixture to heptane and nonane, in a series of hydro-conversion tests of being carried out, under 4.5bar pressure, in the gas phase, the result strong with nonane (low volatility) competitiveness on zeolite catalyst is the same, and the conversion of nonane is all fast than heptane on the catalyst of all researchs; At higher pressure, as 100bar, in the liquid phase, the macroreaction of heptane and nonane is just very approaching, and this shows that it all has higher total concentration on catalyst.With regard to the experiment under the elevated pressures, it can better reflect the intrinsic reactivity energy of various molecules.

Behind test data that obtains two groups of combined multi-stage reactors and limited intrinsic activation energy data, just can set up the performance that a reactor model is used to predict a combined multi-stage adiabatic reactor, then the data that obtain from this composite adiabatic reactor can be used as the test to reactor model again.In addition, from the possibility occurrence and the happening part of adiabatic reactor in service measurable focus or temperature control the heat release Catalytic processes.

In an embodiment of the present invention, also can include laboratory scale detection reaction device, it can be provided with separately or dynamically link to each other with described one or more combined multi-stage tandem reactors, providing, thereby accelerate its process of industrialization about the operation of the different stage reactors of described plural serial stage reactor and the information of performance.Described detection reaction device can be the single-stage piston flow reactor, it also can be the plural serial stage piston flow reactor, itself and described one or more combined multi-stage tandem reactor be arranged in parallel, and by as be provided with an identical temperature control equipment make as described in the detection reaction device with as described in one or more combined multi-stage tandem reactors have identical stationary temperature environment.In addition, can increase or change the component of gaseous state in the arbitrary level that is input to described detection reaction device or liquid material by certain facility.When the detection reaction device is single-stage, can be by the effluent of A reactor coupled in the described one or more combined multi-stage tandem reactors of input in this detection reaction device, together with input quantitative fresh reactant thing and/or product or accessory substance or catalyst poison, determine because the influence of the next stage reactor performance of the reactor of its effluent of input in the change subtend detection reaction device of gaseous state or liquid composition.

When detection reaction device when being multistage, can be mounted with the beds identical in it and can receive identical raw material with described one or more combined multi-stage tandem reactors.The transient response that system produces in the time of so just can utilizing this multistage detection reaction device to measure arbitrary stage reactor in the described corresponding multistage reactor at permanent or temporary change of material component.Such as, by gaseous state or the liquid input that changes the third level reactor in three grades of detection reaction devices, and make comparisons with the performance of corresponding third level reactor in the corresponding combined multi-stage tandem reactor, just can measure the carrying out along with the time, the variation of component is to third level catalyst reactor bed reaction rate and optionally influence.In like manner, change input, just can determine its influence the second level and third level beds to second level detection reaction device.Such as, the speed of the gaseous state material that raising is imported in arbitrary grade of detection reaction device is measured the carrying out along with the time, the result that the variation of this stage reactor performance boost and subsequent reactor produce owing to the change of importing.Like this, can measure arbitrary segment of a beds in plant-scale fixed bed reactors at importing the reaction that changes and produce with regard to being equivalent to.

In an embodiment of the present invention, a plurality of combined multi-stage tandem reactors can be set in parallel in the common stationary temperature environment, and each multistage reactor wherein all can be mounted with identical or different beds, and described beds can be the catalyst granules of identical or different shape or size.Like this, can come to test simultaneously multiple different catalyst, and this catalyst can have different shapes or size.

In addition, in an embodiment of the present invention, a laboratory scale piston flow reactor also can be set, be mounted with in it and at least two interior identical catalyst of described combined multi-stage series connection piston flow reactors, and this laboratory scale piston flow reactor has higher conversion ratio, as 60-80%.The effluent of described laboratory scale piston flow reactor can be imported in the first order reactor in described two combined multi-stages series connection piston flow reactor at least, certainly, also can import certain fresh reactant thing in described first order reactor.Like this, the effluent by adjusting described laboratory scale piston flow reactor and the ratio of fresh reactant thing just can be simulated the characteristics of a big composite catalyst bed different piece of being made up of the beds in all described combined multi-stage tandem reactors.

In addition, two or more laboratory scale detection reaction devices can be set also, itself and described one or more combined multi-stage tandem reactor are set in parallel in the common stationary temperature environment.Like this, just can determine of difference variation in time the reaction that carry out produced of the different piece of described one or more combined multi-stage tandem reactors simultaneously to input.

Two-phase fluidised bed reactor, three phase slurry bed bioreactor or three-phase fluidized bed reactor that the described detection reaction device that dynamically links to each other with the combined multi-stage tandem reactor can be a complete mixing flow.At this moment, by the effluent of the coupled combined multi-stage tandem reactor of control input in complete mixing flow detection reaction device and the ratio of fresh reactant thing, just can simulate the characteristic of single vertical point of described combined multi-stage tandem reactor.

Further, the described detection reaction device that dynamically links to each other with the combined multi-stage tandem reactor also can be a two-dimensional array that is arranged at the microresponse device that separates that is mounted with different catalysts on the glass plate.By this setup, just can determine the essential performance of different catalysts when different mixtures in having fresh reactant thing, effluent and product exists.

In catalysis development device of the present invention, described piston flow reactor can be fixed bed reactors (Fixed Bed Reactors), packed bed reactor (Packed Bed Reactors), trickle bed reactor (Trickle Bed Reactors) and the monolith honeycomb reactor (Monolithic Reactors) of one way or cycling.Described laboratory scale piston flow reactor is meant that the internal diameter of each section reactor of piston flow reactor is less than 101.6mm (4 inches), preferably less than 50.5mm (2 inches), more preferably less than 25.4mm (1 inch); Its length is less than 2.438m (8 feet), preferably less than 1.219m (4 feet), more preferably less than 0.304m (1 foot); Except that crossing the inertia dilution, the useful load of catalyst is less than 800 grams, preferably less than 400 grams, more preferably less than 25 grams.

Like this, by the test under the different test conditions, many characteristics of industrially scalable reactor after just can simulating, thereby the process of quickening industrially scalable.

[description of drawings]

Fig. 1 is the device schematic diagram of combined multi-stage series connection piston flow reactor of the present invention.

Fig. 2 is the device schematic diagram of the plural serial stage detection reaction device of combined multi-stage series connection piston flow reactor of the present invention and setting in parallel.

Fig. 3 be combined multi-stage series connection piston flow reactor of the present invention and with the device schematic diagram of its single-stage detection reaction device that dynamically links to each other.

Fig. 4 is combined multi-stage series connection piston flow reactor of the present invention and dynamically links to each other with it and the device schematic diagram of the plural serial stage detection reaction device that be arranged in parallel.

Fig. 5 is the device schematic diagram that is arranged at a combined multi-stage series connection piston flow reactor with a steady temperature environment of a fluidization sand-bath of the present invention.

Fig. 6 is the device schematic diagram that is arranged at a plurality of combined multi-stage series connection piston flow reactors of a common fluidization sand-bath of the present invention.

Fig. 7 is the device schematic diagram that receives a plurality of combined multi-stage series connection piston flow reactors of controlled variable input of the present invention.

Shown in Figure 8 be the device schematic diagram that is used to simulate the multistage piston flow reactor of isothermal of adiabatic reactor of the present invention.

Fig. 9 is the schematic diagram of an embodiment of reactor of the present invention and separator assembling.

Figure 10 is the schematic diagram of another embodiment of reactor of the present invention and separator assembling.

Figure 11 is the schematic diagram of another embodiment of reactor of the present invention and separator assembling.

[preferred embodiment]

As shown in Figure 1, in first embodiment of the invention, combined multi-stage piston flow reactor 11 is the piston flow reactor of laboratory scale three grades of series connection, and promptly its piston flow reactor 13,15 and 17 by three series connection is formed.Be mounted with corresponding beds 19,21 and 23 in the reactor 13,15 and 17 respectively.In this embodiment, reactor 13,15 and 17 is fixed bed reactors.Between the inlet of the outlet of reactor 13 and reactor 15, between the inlet of the outlet of reactor 15 and the reactor 17 and exit of reactor 17 is respectively arranged with corresponding conveyance conduit (mark) and sampling valve 25,27 and 29.Described sampling valve 25,27 and 29 is provided with outlet 26,28 and 30 respectively, carries out sampling analysis in order to the effluent to respective reaction device 13,15 and 17 respectively.The outlet of described reactor 17 can link to each other with a product collector (not shown) by sampling valve 29.Be usually used in providing the fresh reactant thing source 31 of fresh reactant thing to link to each other with the inlet of reactor 13 by fresh reactant conduit (not mark) to combined multi-stage piston flow reactor 11.In addition, also can a sampling valve (not shown) be set on the fresh reactant conduit between the inlet of fresh reactant thing source 31 and reactor 13, be used for reactant is carried out sampling analysis.

Continuation is referring to shown in Figure 1, and in the present embodiment, multistage fixed bed reactor 11 is arranged in the temperature control equipment 33.In exothermic reaction, in Fischer-Tropsch synthesis, the heat conduction media is housed in the temperature control equipment 33, as circulating boiling water or fluidization sand-bath, be used for the reaction heat of reactor 11 is derived to keep multistage reactor 11 a stationary temperature.In the endothermic reaction, in paraffin dehydrogenation or catalytic reforming reaction, temperature control equipment 33 is provided with heater, as electric heater, in order to give multistage reactor 11 heat supplies so that reactor 11 maintains constant desired temperature.In addition, for existing exothermic reaction the endothermic reaction is arranged again, temperature control equipment 33 can be provided with the fluidization sand-bath and come reactor is operated.

Reactor 13, beds 19 in 15 and 17,21 and 23 can be used for duplicating a longitudinal component of the beds of big fixed bed reactors respectively, the characteristics and the performance of the continuous longitudinal component of big beds measured and analyzed with this, thereby the characteristics of the beds that also can't know at present and vertical distribution of performance measured.In this embodiment, multistage reactor 11 is three grades, it is it reactor that comprises three series connection, certainly, it can be multistage reactor more, and promptly it can comprise more tandem reactor, as four, six etc., like this, just can analyze along the height of a composite catalyst bed, it is the performance of multiple spot more.

The data that obtain according to the reaction of required research and needs, for raw material and reactor 13,15 and 17 effluent can use conventional methods as gas chromatographic analysis/mass spectral analysis (GC/MS), ultraviolet (UV) or infrared (IR) characterize the characteristic of reactant and product, or adopting X-ray diffraction (XRD), infrared diffuse or the known spectroscopy techniques of other industries characterize catalyst system.The attribute of performance of relevant with the beds lengthwise position like this system just can access quantification.And then, just can come optimization system according to the catalytic reaction kinetics information that obtains and the attribute of performance of every bit, such as can according to the catalyst granules different physics that diverse location has in catalyst layer that obtains and chemical property designs catalyst system so that it reaches the yield or the selection rate of maximum in local environment.

The catalyst of filling in the reactor 13,15 and 17 can be catalyst crushing or grained catalyst or commercial size.Reactor amplifies the acquisition of desired data, most of test all is to carry out under isothermy, in order to ensure reactor 13,15 and 17 react under isothermy, available inert particle is to beds 19, catalyst granules in 21 and 23 dilutes, inert particle and catalyst granules, the ratio of the two often for 8-10 than 1.When needs were measured under adiabatic condition, according to the situation of the diameter and the reaction heat of reactor, the catalyst in the beds 19,21 and 23 can carry out the dilution of less degree.Catalyst granules depends on multiple factor with the dilution proportion of particles, as the activity of reaction heat and catalyst granules etc.Certainly, for the industry personnel, for the reaction of given catalyst, reactor diameter and a catalyst particle size, it can determine appropriate catalyst particle and dilution proportion of particles by once simply testing.

Usually, the particle size that is loaded in the commercial size catalyst in the fixed bed reactors is at 1 to 5 millimeter, and catalyst granules has multiple shape, as circle, tubulose, trilobal and annular etc.Crush or powder catalyst is often prepared by the catalyst of commercial size, and its exemplary particles size is at 0.10 to 0.20 millimeter, and certainly, its size under the condition that keeps catalytic performance is the smaller the better.Usually, for being mounted with through for the reactor of commercial size catalyst of dilution, the internal diameter of reactor is 10 times of reduced size in dilution particle or the catalyst granules, and its minimum of a value often is 10-50 millimeter (a 0.4-2 inch).Owing to have a less resistance to mass tranfer, crushing or powder catalyst often than the catalyst activity height of commercial size.So, can have the identical operations temperature with the similar reactor that is mounted with the commercial size catalyst in order to ensure being mounted with reactor crushing or powder catalyst, in being mounted with reactor crushing or powder catalyst, the ratio of inertia dilution particle and catalyst granules is greater than the ratio in the reactor that is mounted with the commercial size catalyst, and is identical with the unit volume thermal discharge (Heat Release Per Unit Volume) of guaranteeing two kinds of catalyst reactor beds like this.

The internal diameter of reactor of catalyst that is mounted with crushing is often for the 5-12 millimeter, and it is less than the internal diameter of the reactor that is mounted with the commercial size catalyst.From the elasticity consideration of multistage reactor 11 different application, the reactor inside diameter of beds that is preferably the crushing that is mounted with usually is identical with the internal diameter of the reactor of the beds that is mounted with required commercial size.In addition, can be by the internal diameter of reactor that thermal conducting sleeve reduces to be mounted with the beds of crushing be set in reactor.

The preferable minimum constructive height of every stage reactor depends on considering of stirring or heat release.In isothermal operation, when stirring into to limiting factor, the selection of height for reactor just needs effectively to avoid the by-pass flow of reactant.Particularly for the reactor that loads the commercial size catalyst, it is 50 times of catalyst granules average diameter highly at least, promptly is 50-250 millimeter (2-10 inch).When reactant passes single- stage reactor 13,15 in the multistage reactor 11 and at 17 o'clock, the conversion ratio of fresh reactant thing constantly increases, and its concentration constantly reduces thereupon.Therefore, when each stage reactor of needs had identical conversion ratio, beds 19,21 in the reactor 13,15 and 17 and 23 thickness just needed constantly to increase.When multistage reactor 11 is operated under adiabatic condition, normal inertia dilution and the large diameter reactor that adopts low ratio.

Referring to shown in Figure 2, it is the device schematic diagram of the second embodiment of the present invention.Among Fig. 2 with Fig. 1 in identical part adopt with Fig. 1 in same numeral.In the present embodiment, its combined multi-stage reactor 11 is identical with the multistage reactor 11 shown in Fig. 1, wherein, present embodiment also comprises another combined multi-stage detection reaction device 35 that be arranged in parallel with described multistage reactor 11, and each stage reactor of this detection reaction device 35 all can be identical with each stage reactor of corresponding multistage reactor 11.Multistage reactor 11 can be arranged in the temperature control equipment 33 with detection reaction device 35, identical among this temperature control equipment 33 and Fig. 1.Certainly, described detection reaction device 35 also can be arranged at and be provided with in another temperature control equipment that the temperature control equipment 33 of described multistage reactor 11 is separated (not shown), like this, just can guarantee that detection reaction device 35 can have different operating temperatures with multistage reactor 11.

Described detection reaction device 35 comprises the reactor 37,39 and 41 of three series connection.Be mounted with beds 43,45 and 47 respectively in this reactor 37,39 and 41.Between the inlet of the outlet of reactor 37 and reactor 39, between the inlet of the outlet of reactor 39 and the reactor 41 and exit of reactor 41 is respectively arranged with conveyance conduit (mark) and sampling valve 49,51 and 53.This sampling valve 49,51 and 53 is provided with outlet 50,52 and 54 respectively, carries out sampling analysis in order to the effluent to respective reaction device 37,39 and 41 respectively.The outlet of described reactor 41 can link to each other with a product collector (not shown) by sampling valve 53.Fresh reactant thing source 31 links to each other with the inlet of reactor 37 by the fresh reactant conduit.In addition, also a control sampling valve (not shown) can be set on the fresh reactant conduit between the inlet of reactant source 31 and reactor 37, its be used for optionally controlling the described multistage detection reaction device 35 of input reactant amount and to the reactant sampling analysis.In addition, reactor 37,39 and 41 inlet are respectively by linking to each other with 59 with a corresponding material source 55,57 of giving to the pipeline (mark) of the selected material of its input.The described material source 55 of giving, 57 and 59 can be used as and are used for the selected material of controlled input respectively and enter reactor 37, facility in 39 and 41, so just can be corresponding determine respectively from the corresponding material of reactor 37,39 and the input of 41 porch all reactors in the multistage detection reaction device 35, reactor 39 and 41 and the Effect on Performance of reactor 41.In the present embodiment, the beds 43,45 and 47 that is preferably detection reaction device 35 respectively with multistage reactor 11 in corresponding beds 19,21 identical with 23.

In the present embodiment, can pass through the input of the relevant reactor of change detection reaction device 35, thereby come the characteristic of the corresponding reactor in relatively this relevant reactor and multistage reactor 11, just the transient response that produces for the permanent or temporary change of input of the arbitrary level that can determine multistage reactor 11 by means of multistage detection reaction device 35.Such as, the gaseous state of the third level reactor 41 by changing detection reaction device 35 or the input of liquid, just can test in multistage reactor 11 in the corresponding third level reactor 23, along with the variation of importing of time to its catalyst bed reaction speed and optionally influence.Accordingly, change the input of the second level reactor 39 of detection reaction device 35, just can detect influence second and third beds 21,23 in the multistage reactor 11.The reaction that is directed to the change of input with regard to arbitrary segment in the beds that equals to detect commercial scale fixed bed reactors like this and produces.Such as passing through to material source 55, increase extra fresh reactant thing in 57 and 59 the corresponding A reactors in multistage detection reaction device 35 and improve the speed of input gaseous state material wherein, just can detect the variation and in time the carrying out of this stage reactor performance boost, the variation that subsequent reactor takes place owing to the variation of its input.

Concerning a selected one-level detection reaction device, can quantize under the substantial length of operation condition described trace components by the concentration of adjusting the trace components in the fresh reactant thing that is input to this stage reactor to material source 55,57 or 59 to the influence of composite catalyst bed different parts.So just can determine vertical position of the key in the recombination catalyst layer in the Industrial Catalysis system.At these positions, catalyst is more easily poisoned or owing to poison inhibitory reaction or generation byproduct is taken place.Behind the specific material of adding provisional in the A reactor of the detection reaction device of other form of selected detection reaction device 35 or follow-up introduction, these detection reaction devices just can be used to the transient response that recombination catalyst layer difference of simulation test produces the temporary variation of the component of this material or upper level reactor effluent, and can monitor in described predetermined substance adition process or after adding this stage reactor and subsequent reactor change (Time Dependent) in time and the reaction that produces.

As shown in Figure 3, be the third embodiment of the present invention, identical label among wherein identical part employing and Fig. 1 with Fig. 1.In the present embodiment, it is provided with a detection reaction device 101, this detection reaction device 101 is the laboratory scale fixed bed piston flow reactor of single-stage, and the selected A reactor in the combined multi-stage fixed bed reactors 11 in its inlet and the present embodiment optionally dynamically links to each other.Between the inlet of the outlet of the first order reactor 13 of multistage reactor 11 and second level reactor 15, between the inlet of the outlet of second level reactor 15 and third level reactor 17 and exit of third level reactor 17 is respectively arranged with valve 103,109 and 115.This valve 103,109 and 115 are provided with outlet 105 respectively, 111 and 117, carry out sampling analysis in order to selectable effluent respectively, simultaneously to respective reaction device 13,15 and 17, described valve also is respectively arranged with another opening 107,113 and 119, in order to selectable the part effluent of corresponding reactor 13,15 and 17 is imported in the detection reaction device 101.The outlet of described reactor 17 can link to each other with a product collector (not shown) by valve 115.Fresh reactant thing source 31 and one can provide for material source 121 and input to described detection reaction device 101.In the present embodiment, be preferably detection reaction device 101 and the beds that loads and multistage reactor 11 in to import the beds of the next stage reactor of its part effluents and loading thereof to detection reaction device 101 identical.Certainly, this detection reaction device 101 can carry out the test identical with the multistage detection reaction device 35 shown in Fig. 2.

Referring to shown in Figure 4, be the fourth embodiment of the present invention, wherein with Fig. 1 and Fig. 2 in identical part employing and Fig. 1 and the identical label of Fig. 2.In the present embodiment, detection reaction device 35 still is combined multi-stage series connection piston flow reactor, and it can be identical with the laboratory scale detection reaction device of the plural serial stage shown in Fig. 2 35.In addition, reactor in the selectable and selected multistage reactor 11 of reactor in the detection reaction device 35 dynamically links to each other, like this, the part effluent of one or more levels reactor of multistage reactor 11 is with regard in selectable one or more levels reactor that is input in the selected detection reaction device 35.Between the inlet of the outlet of the first order reactor 13 of multistage reactor 11 and second level reactor 15, between the inlet of the outlet of second level reactor 15 and third level reactor 17 and exit of third level reactor 17 is respectively arranged with valve 123,129 and 137.This valve 123,129 and 137 are provided with outlet 125 respectively, 131 and 135, in order to selectable to respective reaction device 13 respectively, 15 and 17 effluent carries out sampling analysis, and simultaneously, valve 123 and 129 also is respectively arranged with another opening 127 and 133, in order to selectable in the reactor 39 and 41 in the corresponding detection reaction device 35 of the selected part effluent input of corresponding reactor 13,15.The outlet of described reactor 17 can link to each other with a product collector (not shown) by valve 137.Fresh reactant thing source 31 links to each other with the inlet of reactor 37.In addition, also a control sampling valve (not shown) can be set between the inlet of fresh reactant thing source 31 and reactor 37, its be used for quantitative control be input to detection reaction device 35 the fresh reactant thing and to the sampling analysis of fresh reactant thing.In addition, reactor 37,39 and 41 inlet link to each other for material source 55,57 with corresponding one respectively with 59.The described material source 55 of giving, 57 and 59 optionally import certain material enters reactor 37, in 39 and 41, so just can determine to be input to respectively respective substance in reactor 37,39 and 41 to all reactors in the detection reaction device 35, reactor 39 and 41 and the Effect on Performance of reactor 41.In the present embodiment, the beds 43,45 and 47 that is preferably detection reaction device 35 respectively with multistage reactor 11 in corresponding beds 19,21 identical with 23.

Continuation is referring to shown in Figure 3, and described detection reaction device 101 is complete mixing flow reactor also, but not above-mentioned fixed bed reactors.In complete mixing flow detection reaction device 101, the concentration of raw material thing, product and the distribution of catalyst are identical everywhere, so when this detection reaction device 101 only received effluent from multistage reactor 11, it just was equivalent to a narrow horizontal segment in the beds exit of this stage reactor.Enter the effluent of reactor 11 of complete mixing flow reactor 101 and the concentration ratio between fresh reactant by control, described complete mixing flow reactor 101 just can be simulated the characteristic of selected horizontal segment arbitrarily of the fixed bed reactors of its effluent of input in this complete mixing flow reactor 101.This complete mixing flow reactor 101 can be two-phase fluidised bed reactor, three phase slurry bed bioreactor or three-phase fluidized bed reactor.

Certainly, described detection reaction device 101 also can be selected for use as Y.Jiang etc. at " chemical industry science " (ChemicalEngineering Science) 1999,54 volumes, the two-dimensional catalysts array that discloses in the 2409-2419 page or leaf.Under the condition that different raw materials, effluent and mixture of products exist, a such detection reaction device just can be tested the substantive characteristics of the catalyst of a large amount of crushing.

In the embodiment shown in Fig. 2 of the present invention-4, detection reaction device 35 and 101 can be transfused to one or more in the effluent of selected one-level of fresh reactant thing, multistage reactor 11 and other materials.The impurity that described unclassified stores comprises extra fresh reactant thing, react the gaseous state that generates or liquid product or exist in the fresh reactant thing of industrial-scale reactor in multistage reactor 11.

In an embodiment of the present invention, fluids such as reactant and unclassified stores, product and byproduct of reaction can be gaseous state, liquid state or its mixed state, as gaseous state and the mixing of liquid state or the mixing of two or more immiscible liquid.To containing the fluid of gaseous material, can utilize traditional back pressure regulator and gas flow control system to control with mass flow controller.For quantitative fluid liquid, often select for use as Luo Si holddown (RuskaPump) or syringe pump (Syringe Pump) it is entered in the hyperbaric environment.In addition, in the effluent of reactor 11 or raw material, comprise the multiple fluid state, when particularly immiscible each other water and some hydrocarbons or gas and liquid, just need avoid fluid mobile with piston flow (laminar flow) form.In an embodiment of the present invention, sampling valve can be selected the dynamic sampling valve such as grade that provides as Norway Proserv AS company for use or as United States Patent (USP) the 4th, 035,168 separators that disclosed.Certainly, also can use static mixer that Proserv AS company provides that the fluid of needs sampling is stirred samples to it rapidly after multi-mode fluid is evenly mixed.Between the immiscible raw material or between the effluent of raw material and reactor, when it is admitted to reactor, perhaps as in a multistage reactor, conveying has multi-mode effluent when entering the inlet of subsequent reactor from what the outlet of a reactor was discharged, fluid-transporting tubing needs higher Reynolds number, and its principle just is similar to the fuel injection system of automobile engine.Certainly, also can use ProservAS company or be positioned at the Admix company in Manchester, New Hampshire city the agitator that provides to realize the abundant mixing of different fluid, like this under the situation, having needs to do some simple tests often and guarantees that fluid is flowed through and evenly mix behind the described device.When sampling, regular meeting is provided with the sample memory that links to each other with reactor by double block valve, and this sample memory is in the environment of normal pressure or a little higher than normal pressure.After gaseous material and liquid fully mix in conveyance conduit, open double block valve and make mixed fluid enter sample memory, close double block valve then and remove sample memory and sample is wherein analyzed.There is certain density inert gas in regular meeting in sampling and analytic process, and as argon gas, it helps the material balance of fluid, so that convection cell carries out Accurate Analysis.When described fluid does not fully mix, just gas-liquid separator need be set, then by gaseous material and liquid being analyzed respectively as the overall Carbon balance analytical method of helium or argon gas internal reference method and related gaseous material and liquid, at this moment, this situation can thereunder be provided with the fluid sample memory and finish by the gaseous sample memory is set above conveyance conduit.

When the characteristic of research piston flow reactor, what pay particular attention to is absorption or the reaction at catalyst surface of raw material components, product or accessory substance.Such as, in the synthetic and hydrocracking reaction, materials such as ammonia, carbon monoxide and hydrogen sulfide can take the activity of such catalysts position, reduce reaction rate and influence to product selectivity at cobalt-based catalysis Fischer-Tropsch.The reaction that is caused by this class material often needs the regular hour to reach balance, and after removing this type of material in from the material to the reactor, the reacting recovery original state also needs to spend the regular hour.

Ammonia be known can be synthetic and the material of hydrocracking catalyst reaction with co-based fischer-tropsch, it can cause the reduction even the inefficacy of catalyst activity.Except in raw material except that deammoniation, often utilize hydrogen to remove the ammonia of catalyst surface.In order to test the influence of ammonia different parts in composite catalyst bed, can add a certain amount of ammonia in arbitrary grade porch of a detection reaction device, so just can reproduce owing to the existence of ammonia in the raw material the influence at the selected position of recombination catalyst layer.Control the transform level at selected catalyst position by the dividing potential drop of adjusting temperature, rate of flow of fluid or reactant in this grade detection reaction device, so just can determine the influence of ammonia under different reaction conditions.In addition, for by the composite catalyst of ammonia pollution, by adjusting in the input detection reaction device concentration of hydrogen in one or more levels, so also can test of the influence of ever-increasing hydrogen, as the lost efficacy position of maximums of those catalyst activities to the composite catalyst different parts.

For carbon monoxide, it can tightly cover on the Co based Fischer-Tropsch synthesis catalyst surface, thereby reduces the surface that hydrogen can be used, and becomes a factor of restriction hydrogen reaction speed.By hydrogen and the concentration ratio of carbon monoxide and the performance of more described detection reaction device and multistage reactor 11 corresponding reactors in the raw material of adjusting input in selected detection reaction device 35 and 101, the change in concentration that just can test hydrogen and carbon monoxide is to reaction rate and optionally influence.By adjusting the dividing potential drop of temperature, rate of flow of fluid or reactant in the detection reaction device, like this, utilize multistage detection reaction device just can test the influence under differentiated yields of hydrogen and carbon monoxide.

Be known that at present at the Fischer-Tropsch of piston flow reactor synthetic and heavy oil concentrates and conversion process in the water that increases reaction rate is had positive effect.By add quantitative water and the detection reaction device of relatively being correlated with and the performance of the corresponding reactor in the multistage reactor 11 in selected detection reaction device 35 or 101, the water that just can study adding is to recombination catalyst layer selected vertical position reaction rate and optionally influence.

In the reaction of hydrotreatment, utilize mensuration Joseph Conrad inferior (Conrad son) carboloy residue to detect the effect of hydrotreatment usually.Wax also can form certain influence to fischer-tropsch synthetic catalyst.Usually, in Fischer-Tropsch synthesis,, will stop reactant to leave catalyst surface to catalyst surface diffusion and product in case carbon and heavy wax are deposited on the catalyst.Like this, some side reactions (Side Reaction) take place with regard to regular meeting in the reactant of the sediment of catalyst surface or not diffusion, thereby reduce activity of such catalysts.At beds is under the situation of commercial size catalyst, because the evolving path of commercial size catalyst is very long, under the limited easily condition of diffusion, will influence the bulk life time of catalyst and the performance that needs very high cost to remove maintenance system.Certainly, by adding the above-mentioned substance of different molal weights (Molecular Weight Fractions) in certain level or 101 in selected detection reaction device 35, just can determine its having the greatest impact to which part in the recombination catalyst layer.In addition, also can be by can be to feeding the effect that hydrogen, water or lightweight solvent are determined different catalyst regeneration technology in the relevant detection reaction device that contains above-mentioned substance, thus definite catalyst regeneration technology preferably.These come from tar sand, shale for those processing, and the heavy charge of heavy oil precipitation and coal etc. is most important.Contain many pollutants that make catalyst poisoning at these heavy charges,, consider that from economic feasibility in-situ regeneration is unique method often just for the increase that reduces to remove to change the cost that fouled catalyst brings through fresh catalyst commonly used.

In addition, polynuclear armatic hydrocarbon also is the present known material that can influence catalyst performance.It reduces activity of such catalysts and selectivity in the hydrogenation treatment by form the carbonaceous cover layer on the catalyst activity position.By in selected detection reaction device 35 or 101, adding the performance of the corresponding reactor in polynuclear armatic hydrocarbon and comparison and the multistage reactor 11, just can determine the influence of the different longitudinal position of its recombination catalyst layer in piston flow reactor.Such and then definite polynuclear armatic hydrocarbon to which position of recombination catalyst layer has the greatest impact, thereby can take corresponding method to improve the design of system and the performance of raising catalyst.

Referring to shown in Figure 5, in the present embodiment, combined multi-stage piston flow reactor 501 is laboratory scale fixed bed reactors, and its reactor 503,505 and 507 parallel to each other by three and series connection is formed.Reactor 503,505 and 507 is arranged in the fluidization sand-bath 509 of a heating or cooling jointly, makes its apparatus structure compact more.Gaseous reactant from raw material source 511 output back by the fresh reactant conduit and enter the inlet of first order reactor 503 after through a heater coil 513; Also can be after liquid material (may be reactant) is exported via charging pump 515 through entering the inlet of first order reactor 503 behind the heater coil 513.Described heater coil 513 can be arranged in the fluidization sand-bath 509, and it is in order to be heated to suitable temperature to gaseous state and liquid material.In addition, can on the pipeline of carrying gaseous state and liquid material, sampling valve (not shown) be set, so that material is carried out sampling analysis.Between the inlet of the outlet of reactor 501 and reactor 505, between the inlet of the outlet of reactor 505 and the reactor 507 and exit of reactor 507 can be respectively arranged with sampling valve 517,519 and 521, and the outlet of reactor 507 can link to each other with a separator 523 by sampling valve 521.Sampling valve 517,519 and 521 all offer an opening (not mark), in effluent to the detection reaction device 525 in order to selectable conveying respective reaction device, simultaneously these sampling valves also can be provided with another opening (not shown), in order to the effluent of carrying the respective reaction device to device that this opening links to each other in.

Referring to shown in Figure 6, present embodiment has disclosed the connect device schematic diagram of laboratory scale piston flow reactor 531,533 and 535 of three combined multi-stages.These multistage reactors are arranged in the common fluidization sand-bath 537.Described multistage reactor 531, reactor in 533 and 535 is all with the set-up mode identical with reactor in the multistage reactor 501 that discloses among Fig. 5 and setting parallel to each other, and can before each multistage reactor, all be provided with Fig. 5 in identical heater coil 513.In the present embodiment, also be provided with a single-stage detection reaction device 538, it is arranged in the fluidization sand-bath 537 equally, and it can be and the 101 relevant any type of reactor of detection reaction device shown in above-mentioned Fig. 3.Detection reaction device 538 is between multistage reactor 533 and 535, be provided with therebetween and sampling valve 517 as shown in Figure 5,519 are connected this detection reaction device 538 and multistage reactor 533 and 535 with 521 identical sampling valves, detection reaction device 538 just can optionally receive the effluent of certain stage reactor of selecting in reactant or multistage reactor 533 and 535 like this.Raw material source 539,541,543 and 545 provide reaction mass to corresponding reactor 531,533,538 and 535, and identical reaction mass can be provided respectively.In addition, the outlet of the outlet of reactor 531,533 and 535 afterbodies and reactor 538 links to each other with 551 with the separator of correspondence or product collector 547,549,553 respectively.Certainly, these outlets also can all be connected to a common separator or product collector.

Referring to Fig. 5 and shown in Figure 6, the degree of depth when the parallel set-up mode of described reactor in the fluidization sand-bath makes sand-bath not need all vertically to be provided with as reactor, and sampling valve 517,519 and 521 is arranged at outside the sand-bath, is convenient in the operating process of reactor it be safeguarded and regulate.When the effluent of certain stage reactor in the multistage reactor has the multiple fluid state, the pipeline that connects this stage reactor outlet and next stage reactor inlet just need have higher Reynolds number or use static agitator (Static Mixer) to form piston flow to avoid the fluid in the pipeline, on the other hand, sampling valve 517,519 and 521 dynamically sampling valve such as can adopt, and other that can be also perhaps that the present invention describes form the mode of piston flow to avoid fluid.

Be arranged at a common temperature control equipment by a plurality of multistage reactors, as fluidization sand-bath 537 or as the described temperature control equipment of Fig. 2-4, just can measure the different qualities of a Catalytic processes simultaneously, and then accelerate its process of industrialization.With Fig. 6 is example, and multistage reactor 535 is mounted with the catalyst granules through the crushing of inert substance dilution, and multistage reactor 533 is mounted with the catalyst granules through the commercial size of inert substance dilution, and it is all being operated under isothermy.In addition, multistage reactor 531 is mounted with the catalyst granules of a certain amount of commercial size, and it is operated under adiabatic condition.Like this, dynamics, the matter that just can obtain simultaneously in the Catalytic processes by the reactor of operating under isothermy pass and heat biography characteristic, and can be verified the reactor model that the data that obtained by isothermal reactor are set up by the data that adiabatic reactor obtains.

In addition, also can help amplify a Catalytic processes by additive method, such as the characteristic of testing multiple different catalysts simultaneously, perhaps relatively be arranged at a plural serial stage reactor of the catalyst that is mounted with crushing in the identical constant temperature unit and be mounted with other plural serial stage reactors of catalyst of the commercial size of difformity and size.In addition, come continuous test by in the different stage reactors of plural serial stage reactor 11, being mounted with different catalyst, like this, just can design the composite catalyst bed of a multilayer, and the intrinsic propesties of its each catalyst layer all is complementary with local dynamics and quality delivery context, with this W-response of system is changed along the longitudinal, and then the optimum process performance at each vertical position of definite reactor.By being set, a plurality of plural serial stage reactors can parallelly determine different heat-removal capability in the independent temperature control equipment of controlling separately.

Referring to shown in Figure 7, reactor module 151 includes the laboratory scale piston flow reactor 151-1 that be arranged in parallel to 151-n.A temperature control equipment 152 is controlled reactor 151-1 to 151-n temperature on every side around being arranged at module 151.An exothermic reaction, in Fischer-Tropsch synthesis, the heat conduction media is arranged in the temperature control equipment, as circulating boiling water, be used for deriving the reaction heat of reactor 151-1 to 151-n.An endothermic reaction, as be dehydrogenated to that ring obtains that aromatic (Dehydrocycloaromatization), fluid are reformed or hydrotreatment in, temperature control equipment is provided with heater, as electric heater in order to give reactor 151-1 to the 151-n heat supply.Certainly, for existing exothermic reaction the endothermic reaction is arranged again, temperature control equipment 152 can be provided with fluidization sand-bath heater and come corresponding reactor is operated.

Reactor 151-1 is mounted with corresponding beds 153-1 respectively to 153-n to 151-n.Reactor module 155 can be identical with module 151 with 157, its comprise respectively the piston flow reactor 155-1 that be arranged in parallel to 155-n and 157-1 to 157-n.Reactor 155-1 be mounted with respectively to 155-n and 157-1 to 157-n corresponding beds 159-1 to 159-n and 161-1 to 161-n.As shown in Figure 7, the outlet of the reactor in the module 151 links to each other by the inlet of reactor corresponding in conveyance conduit (mark) and the module 155, and the outlet of reactor is also continuous by the inlet of the corresponding reactor in conveyance conduit and the module 157 in the module 155.Like this, Chuan Lian reactor 151-1 successively, 155-1 and 157-1 have just formed combined multi-stage series connection fixed bed reactors, and in like manner, other corresponding successively reactors have also formed combined multi-stage series connection fixed bed reactors.In the present embodiment, module 151,155 and 157 can be respectively arranged with requisite number purpose parallel reactor, is provided with 4 or 8 or 16 reactors such as, each module is parallelizable.Certainly, the module of different numbers can be set as required also, as 4 or 6, the reactor in the module is continuous to link to each other with previous reactor and subsequent reactor correspondence.

Temperature control equipment 158 and 160 is arranged at respectively around module 155 and 157, and this temperature control equipment 158 can be identical with temperature control equipment 152 with 160, and perhaps itself and temperature control equipment 152 are exactly a common temperature control equipment.Be respectively arranged with between the inlet of corresponding reactor and on the conveyance conduit of the outlet of the reactor in the module 157 in the outlet of the reactor in module 151 and the module 155 between the inlet of corresponding reactor, in the outlet of the reactor in the module 155 and the module 157 corresponding sampling valve 163-1 to 163-n, 165-1 to 165-n and 166-1 to 166-n.Fresh reactant thing source 167 is imported quantitative fresh reactant thing through fresh reactant conduit (not mark) corresponding reactor 151-1 in module 151 to the inlet of 151-n to 169-n by control valve 169-1.Piston flow reactor 171 also can receive the fresh reactant thing from fresh reactant thing source 167, and the outlet of this reactor 171 through conveyance conduit respectively with module 151 in corresponding reactor 151-1 link to each other to the inlet of 151-n, by control valve 173-1 to 173-n in order to the quantitative effluent that comes autoreactor 171 to these reactor inputs.As shown in Figure 7, described reactor 171 is arranged at outside temperature control equipment 152,158 and 160, so reactor 171 also may be defined as external reactors.Certainly, it also can be arranged in the described temperature control equipment.

In the piston flow reactor of a commercial size, along the thickness of beds, the ratio of fresh reactant thing, product and accessory substance is constantly to change.In the porch of reactor, the fresh reactant thing accounts for 100%, and product and accessory substance all are zero.Along with the consumption of fresh reactant thing in beds, along beds, the ratio of fresh reactant thing reduces, and it is big that the ratio of product and accessory substance becomes.In device shown in Figure 7, can carry out multiple test, the component of all loading identical catalyst and material such as all reactors constantly changes to another level from A reactor, and perhaps the size of catalyst granules or framework are all different in can receiving each stage reactor of identical input.

Dynamics

Up to now, only be to be undertaken to the kinetic measurement of fixed bed reactors by inlet and exit measurement to beds, this mensuration is exactly the equalization for the catalyst bed layer thickness in fact.When the dynamics of analysis reactor, general earlier the dynamics progression of reaction is supposed, and often supposed in reactor and remain unchanged, yet under many circumstances, this supposition is incorrect along catalyst bed reaction progression.By means of the plural serial stage piston flow reactor shown in Fig. 1 of the present invention-7, just can measure in reactor thickness direction, the dynamics of laminar flow catalysis system situation of change longitudinally along beds.

With device shown in Figure 7 is example, uses plural serial stage reactor in the present embodiment and method just can develop in reactor along the data that are used to amplify of integration, differential and the intrinsic kinetics of the beds laminar flow catalysis system relevant with lengthwise position.In order to determine the integration dynamics of a fixed bed reactor system, at module 151,155,157 and reactor 171 in be mounted with the required beds of system.The reactor 151-1 that be arranged in parallel in the module 151 can receive the fresh anti-material and the effluent that comes autoreactor 171 from fresh reactant thing source 167 of different proportion to 151-n.Such as, by control valve 169-1 to 169-n and 173-1 to 173-n, make reactor 151 only receive 100% fresh reactant thing, reactor 151-2 can receive the fresh reactant thing and the ever-increasing effluent of continuous minimizing to 151-n.Like this, flow reactor 151-1 just is equivalent to the continuous fragment at regular intervals of tool to each other (slice) of the beds of fixed bed reactors respectively to 151-n.Wherein, reactor 151-1 is equivalent to a section of beds porch, and reactor 151-2 is equivalent to along other continuous of beds and vertical section at regular intervals to each other to 151-n.Like this, module 155 and 157 just can be used for the catalyst section between the continuous beds in module 151 in the fixed bed reactors is provided the data of amplification.Certainly, in the present embodiment, the ratio that is preferably fresh reactant thing in the effluent of reactor 151-n should be greater than the ratio of the fresh reactant thing in the material of importing in reactor 152-1.As having 90% conversion ratio when reactor 171, comprise 10% fresh reactant thing so at its effluent of its exit, remaining is product and accessory substance.When reactor 151-2 receives the effluent of reactor 171 of 88% fresh reactant thing and 12%, in the material component of the porch of reactor 151-2,89.2% fresh reactant thing is arranged, remaining is product and accessory substance.As reactor 151-1,155-1 and 157-1 all have 3% conversion ratio, and their effluent comprises 97%, 94.1% and 91.3% fresh reactant thing respectively so, and remaining is product and accessory substance.Like this, the component of fresh reactant thing, product and accessory substance and ratio just are equivalent to component and ratio in continuous vertical section an of beds in the fixed bed reactors in the module 151,155 and 157.

In order to determine the integration dynamics of the catalysis system that forms by combined multi-stage series connection fixed bed reactors that lengthwise position with beds is relevant, just be necessary that each continuous vertical section of beds such as the every standard liters of analysis under standard temperature and pressure (STP) (STP) enters the mouth and the material fluid and the component in exit.What what for instance, in Fischer-Tropsch synthesis, just need to measure hydrogen and the carbon monoxide that under normal temperature and pressure (STP), has consumed mole in each reactor and generated product and accessory substance.Then to conversion ratio or have other amounts of same meaning, as when reactant during by development of evil in febrile disease agent bed along the concentration of beds corresponding to the remaining fresh reactant thing of continuous lengthwise position, draw with respect to the time.Like this, along resulting figure, the slope of its every bit is exactly system's reaction rate at that time.And then, draw log-log graph to reactant rate with along the concentration of the fresh reactant thing of beds.If curve map is a straight line, integration dynamics progression (integral kinetics) along catalyst bed system is a constant so, when it is horizontal linear, system is a first order reaction, when the slope of straight line is positive number, system is the positive order reaction greater than 1, and when being negative, system is negative order reaction.

When log-log graph is not straight line, the integration dynamics of illustrative system constantly changes along the thickness of beds, and just need utilize regression analysis (RegressionAnalysis) that curve map is matched each other with the formula relevant with reaction rate and fresh reactant substrate concentration this moment.Then formula is carried out differential, utilize drawing or mathematical method to provide Rate Models and correlation along the lengthwise position of beds.Drafting method can be referring to John M.Chambers, " the data analysis drafting method " of Chapman and Hall (Graphical Methods forData Analysis), May nineteen eighty-three, ISBN:0412052717.

In order to determine temperature and pressure to system's integration effect of kinetics, above-mentioned test can be carried out under different temperature and pressures.In addition, also can use the catalyst of different size, as the crushing of the catalyst of industrial size and shape and dilution or powder catalyst.

Use the apparatus system shown in Fig. 1-7, can not consider that matter passes and heat passes under the condition of influence the differential driving force of originally seeking peace of combined multi-stage series connection fixed-bed catalytic system learned and tests, to accelerate the process of industrialization of system.With device shown in Figure 7 is example, and the beds that loads in the reactor uses through the influence small crushing of dilution or that the powder catalyst particle avoids heat biography and matter to pass.In addition, the thickness of catalyst reactor bed is everlasting 5-10 centimetre, and the diameter of reactor is less is advisable, usually at the 5-12 millimeter, equally to avoid heat to pass influence.Certainly, can be by the internal diameter that thermal conducting sleeve reduces reactor be set in reactor.Can adopt said method successively for the dynamic (dynamical) measurement of system's integration.Determine differential driving force class hour of system when needs, the conversion ratio of each stage reactor all needs very little, as less than 20%, is preferably the conversion ratio that has only 2-5% in Fischer-Tropsch is synthetic.Equally, test can be carried out under different temperature and pressures to determine the influence of temperature and pressure to system's intrinsic and differential driving force.

Also can be used in as Fig. 1 or other reactor assemblies shown in Figure 5 for the above-mentioned kinetic measurement method of example with Fig. 7, as long as this reactor assembly has and enough multistage can provide composite catalyst bed required vertical information tandem reactor.In reactor assembly shown in Figure 7, reactor 171 can be imported its effluent by all reactors in module 151, like this, each reactor in the module 151 just can receive same accurate product, accessory substance and trace components (Trace Element), thereby can more accurate reactor condition that is virtually reality like reality and reduce the error that the change owing to material component produces.In addition,, can sample simultaneously for the input and output of the reactor in all modules at Fig. 7, be convenient to particular moment reactor performance analyze; Certainly, repeated sampling that also can be regular in the reactor running with the performance of assaying reaction system and the relation in reaction time, and then understands that those performances have taken place to change and which situation has taken place the longitudinal region of whole beds.These data are very useful for stability and other characteristics of research catalyst.

According to different goals of the invention, as amplification or other purposes etc., reaction unit of the present invention can be used to detect the operating parameter of piston flow reactor under various objectives.Such as, under the condition of different reaction temperatures, pressure, catalyst shape and size, the activity that detection is associated with longitude and the relation in reaction time.Certainly also can detect the technological parameter that other are associated with longitude, these technological parameters comprise different air speeds, reactant and side reaction thing, different operating temperature and pressure, reaction time, different catalyst size and shape and conversion ratio, yield, dynamics and selection rate; The parameter that also has catalyst physics and chemical characteristic to change in addition is as the growth of active sites crystallization size, oxidation and active sites surface coating etc.

Utilize reaction unit of the present invention, can accelerate the process that is found to its commercial application at first from Catalytic processes.For instance, in one embodiment of the invention, four multistage reactors be arranged in parallel.Wherein, the reactor in first multistage reactor all is mounted with the catalyst of crushing, and like this, this multistage reactor just can be used to provide intrinsic reaction rate and selective data.Reactor in second multistage reactor all is mounted with the catalyst of commercial size.When all reaching given conversion ratio, direct comparison based on to the time of staying that reactant is relative in the reactor of the reactor and the commercial size catalyst that are mounted with the crushing catalyst just can come to determine the degree that the matter biography blocks in the data that second reactor obtains.By acquisition, just can determine efficiency factor (Effectiveness Factor), and then definite effective diffusivity is with respect to the relation of the conversion ratio or the time of staying at a series of pairing conversion data of the time of staying.Simultaneously, these data also can provide matter to pass optionally influencing information.The 3rd multistage reactor also can be single-stage reactor, and it is as the detection reaction device.This detection reaction device is reactor or the complete mixing flow reactor that is mounted with more shallow beds, and can directly import in the relevant detection reaction device from the fluid of the arbitrary reactor in aforementioned two multistage reactors.In addition, also can in the detection reaction device, import other gas or liquid to determine the rate of adsorption or the catalyst surface changes of properties of catalyst.These information have very big value to the model of setting up fixed bed reactors.At last, the 4th multistage reactor, it is an adiabatic reactor, is used for testing the performance of the reactor model that is come by the development of previous reaction device.The pattern of this parallel operating series reactor can obtain to amplify required data fast.In fact, even under a temperature, obtain the data of the amplification that is useful on that comprises catalysqt deactivation (Deactivation) and playback of data thereof at present, often need the time of 1-2, yet, utilize device of the present invention just can save the research and development time of several years quickly.Another benefit of the present invention is to operate many bank of reactor simultaneously, and can operate under different temperature, pressure and material component.In addition, device of the present invention can produce optimum economy for industrialization design, the cost of saving in its industrialized process compared with new catalyst of quick amplification, the cost of the tandem reactor that the many groups of operation simultaneously be arranged in parallel is still very little, can make and produce every barrel of oil and save 1 dollar such as developing a kind of novel catalyst, the factory of 100,000 barrels of dailys output just can save above 3,000 ten thousand dollars in 1 year so.Clearly, these savings can be easily more than offset the cost that falls to operate the many groups tandem reactor that be arranged in parallel.

In adiabatic reactor, the temperature in the reactor constantly changes, and controls just may produce focus when bad and the temperature runaway phenomenon takes place.Simultaneously, because the response parameter in the adiabatic reactor is in the continuous variation, like this,, just can not obtain in the adiabatic reactor specifically as this reactor of direct measurement, information accurately.The reactor that a complete adiabatic reactor is divided into plural serial stage helps to study the information of diverse location in the beds.Yet the continuity of controlling the response parameter between the adjacent two-stage reactor will face difficulty.

Therefore, directly just may be difficult to obtain the characteristics such as dynamics, matter biography and heat biography of adiabatic reactor by the characteristic that detects adiabatic reactor.

As shown in Figure 8, in one embodiment of the invention, it utilizes laboratory scale isothermal reactor to simulate to be mounted with the characteristic in the adiabatic reactor of same catalyst bed, so just cost that can the be lower Catalytic processes of a kind of industrial adiabatic reactor of exploitation fast.In the present embodiment, described laboratory scale isothermal reactor is a combined multi-stage piston flow reactor 607, and its reactor 61,63 and 65 parallel to each other by three and series connection is formed, and is mounted with catalyst bed interval 62,64 and 66 in it respectively.Definable reactor 61,63 and 65 is respectively the first order, the second level and third level reactor.Raw material source 60 links to each other with the inlet of first order reactor 61 by fresh reactant conduit 70; Between the inlet of the outlet of reactor 61 and reactor 63, between the inlet of the outlet of reactor 63 and the reactor 65 and exit of reactor 65 can be respectively arranged with sampling apparatus 67,68 and 69, and the outlet of reactor 65 can link to each other with a separator (not shown) by sampling valve 69.Sampling apparatus 67,68 and 69 also offers an opening 601,602 and 603 respectively, in order to the effluent of carrying the respective reaction device to device that this opening links to each other in.In addition, also can fresh reactant conduit 70 being provided with sampling apparatus (not shown) comes fresh material is carried out sampling analysis.Be respectively arranged with temperature control equipment on reactor 61,63 and 65, it comprises that first, second and third temperature control equipment 604,605 and 606 is in order to control the temperature of respective reaction device 61,63 and 65 respectively.In the present embodiment, described reactor 61,63 and 65 all can be operated under isothermy.In addition, can be provided with preheating device (not shown),, also can in first order reactor 61, be provided with preheating device certainly in order to raw material is heated to suitable temperature in raw material source 60 and 61 of first order reactors.

Because the length temperature along reactor in adiabatic reactor is constantly to change, so when simulating the catalysis characteristics of an adiabatic reactor, just need at first to determine the temperature of the temperature control equipment on each grade isothermal reactor with multistage isothermal reactor.Usually, can determine the caused temperature variations that reacts in the temperature of the temperature control equipment on the first order reactor and the first order reactor earlier in given reaction condition and the data under the Catalytic processes by what operate in practice that adiabatic reactor obtains, as the situation of intensification/cooling; And then the temperature by the temperature control equipment on the first order reactor and in course of reaction the variations in temperature in the first order reactor determine the control temperature of second level reactor; Determine control temperature of third level reactor or the like by calculating then to second level reactor.Like this, after the temperature of each temperature control equipment was determined, described isothermal reactor just can be simulated the characteristic of adiabatic reactor.

In the present embodiment, the temperature of first temperature control equipment, 604 control first order reactors 61 is T1; The temperature of second temperature control equipment, 605 control second level reactors 63 is T2; The temperature of the 3rd temperature control equipment 606 control third level reactors 65 is T3.Wherein, T1, T2 are different with T3.Certainly, determine corresponding different temperature T 1, T2 and T3 or use a common temperature control equipment to control the temperature of every stage reactor 61,63 and 65 respectively according to different application and operating condition.

Like this, in the present embodiment, just can be by the first order, the second level and the third level reactor 61 that is isothermal reactor, the characteristic of the different continuous catalyst bed interval in 63 and 65 beds of simulating respectively in the adiabatic reactor, thereby can obtain by catalyst bed interval 62,64 and the 66 Catalytic processes characteristics of forming that are loaded into a composite catalyst bed in the adiabatic reactor.Because the ease for operation of isothermal reaction in the present embodiment, just can be simulated an operational characteristic in plant-scale adiabatic reactor by comparatively simple, safe mode by isothermal reactor.

Operating the continuous piston flow reactor of two-stage at least, such as when a complete beds being divided into multistage catalyst bed interval, the effluent of upper level reactor will be through entering in the next stage reactor behind one section conveyance conduit, like this, the effluent that guarantees the upper level reactor still keeps the continuity or the uniformity of parameter of materials when entering in the next stage reactor behind the conveyance conduit, and the variation that material state etc. do not take place just seems extremely important.

In a specific chemical technology and given following time of reaction condition, when the effluent of A reactor is a homogeneous phase, promptly single phase, during as the gas phase attitude, often this homogeneous phase effluent just can directly transmit by the conveyance conduit between the superior and the subordinate's reactor.In addition, in some reactions, described effluent is heterogeneous, and is typical in gas phase and liquid phase.Described gas phase can comprise gas, steam or its mixture; May include water, oil phase, other things that do not dissolve each other in the described liquid phase and reach emulsion etc. mutually.

Usually, have a plurality of different material components in the heterogeneous effluent, and material component has separately state in each.When the material component in the described heterogeneous effluent was in thermodynamical equilibrium (Thermodynamic Equilibrium) between described gas phase and liquid phase, this effluent also can directly transmit by the conveyance conduit between the superior and the subordinate's reactor.

Yet, some the reaction in, as hydrodesulfurization reaction (Hydrodesulphurization, HDS) in, the material component in the heterogeneous effluent is not in thermodynamic equilibrium state.At this moment, if the heterogeneous effluent of discharging from the upper level reactor directly is transported in the process of next stage reactor by conveyance conduit, material component wherein, the states such as dividing potential drop of component just may change, thereby the effluent of upper level reactor just can not keep the continuity or the uniformity of parameter of materials when entering in the next stage reactor.Like this, for the measurement of Catalytic processes and optimization, just may have bigger adverse effect.

In one embodiment of the present of invention as shown in Figure 9, it can well keep material transmission continuity or uniformity in the heterogeneous fluid transmission course.In the present embodiment, combined multi-stage piston flow reactor 707 can be laboratory scale piston flow reactor, and its reactor 71 and reactor 73 parallel to each other by two and series connection are formed.Definable reactor 71 is a first order reactor, and definition reactor 73 is a second level reactor.Be mounted with beds 72 and 74 in the reactor 71 and 73 respectively, be respectively arranged with temperature control equipment 701 and 702 on it, this temperature control equipment 701 can be identical with 702, also can be different.Raw material source 70 can be conveyed into raw material in first reactor 71 by feed line road 77.In the present embodiment, also be provided with a separator 703 at first reactor 71 and 73 of second level reactors.The exit of first order reactor 71 is provided with effluent pipeline 78, and it can link to each other with the inlet of described separator 703.Simultaneously, separator 703 is provided with gas-phase transport pipeline 75 and links to each other with the inlet of second level reactor 73 respectively with liquid phase conveyance conduit 76; The exit of second level reactor 73 also is provided with effluent pipeline 78.When reacting, raw material enters in the first order reactor 71 and reacts, the heterogeneous effluent of first order reactor enters in the described separator 703 and is separated into gaseous fluid and liquid phase fluid, subsequently, gaseous fluid and liquid phase fluid enter the reaction of carrying out next step in the reactor of the second level via gas-phase transport pipeline 75 and liquid phase conveyance conduit 76 respectively.

As shown in Figure 9, in an embodiment of the present invention, the flow resistance that a current-limiting apparatus 705 is controlled gaseous fluid is set on conveyance conduit 75, on gaseous fluid, to produce pressure differential.Suppose that the pressure on first order reactor 71 and the separator 703 is P1; At this moment, because the existence of current-limiting apparatus 705, the pressure of second level reactor 73 is P2 just, and P1〉P2.Like this, on gas-phase transport pipeline 75, just produced a pressure differential Δ P=P1-P2.Because the existence of pressure differential (pressure drop) Δ P, when this Δ P is enough to overcome the frictional force in the liquid phase conveyance conduit 76 and/or enters the gravity of the liquid phase fluid in the liquid phase liquid phase conveyance conduit 76, just can be pressed into liquid phase conveyance conduit 76 to liquid phase fluid and then enter in the second level reactor 73.It is very little and be unlikely to influence follow-up reaction like this, just can to drive liquid phase fluid and this pressure differential by means of the pressure differential Δ P that produces on the gaseous fluid.Described current-limiting apparatus 705 can be a flow-limiting valve, aditus laryngis or other current-limiting modes etc.Behind the gas-phase transport pipeline of selecting suitable dimension and shape, as capillary etc., this pipeline itself is also just controlled the flow resistance of gaseous fluid to play the effect of current limliting as current-limiting apparatus 705.

In addition, in the present embodiment, can be on current-limiting apparatus 705 or gas-phase transport pipeline 75 two ends be provided with the variation that differential pressure pickup (not shown) is measured pressure differential deltap P.By the physical characteristic of Δ P and gaseous fluid, just can calculate the information of gaseous substance.

Continuation is referring to shown in Figure 9, and when Δ P is too for a short time when being not enough to drive liquid phase fluid, described liquid phase fluid will constantly accumulation in separator 703; When Δ P was enough big, liquid phase fluid will constantly be pressed in the second level reactor 73 and all be pressed into up to all liquid phase fluids.In the time of in all liquid phase fluids all are pressed into second level reactor 73, gaseous fluid will enter in the second level reactor 73 from liquid phase conveyance conduit 76, like this, Δ P will descend, and liquid phase fluid will be accumulated again along with the carrying out of reaction and occupy liquid phase conveyance conduit 76.Δ P can return to predetermined value again subsequently, and liquid phase fluid can be pressed empty again.Like this, owing to be input to the raw material of first order reactor 71 and the limitation of reaction, often just be difficult in the balance of keeping liquid level 704 in the separator 703, and can not keep the liquid and gas fluid to supply uniformly, its flow is in the continuous fluctuation, is very disadvantageous to subsequent reactions like this.

In a preferred embodiment, in described separator 703, be provided with the variation that liquid level inductor 706 is used for monitoring liquid level 704, simultaneously, the signal of these liquid level inductor 706 outputs can be used to control described current-limiting apparatus 705, drive liquid phase fluid to produce suitable Δ P, so that liquid level 704 is in preposition.So just can avoid the fluctuation of liquid and gas fluid, be convenient to the carrying out of subsequent reactions.It is contactless, optics, laser induced etc. that described liquid level inductor can adopt.Be preferably and use the non-contact optical induction installation.Like this, when realizing that liquid phase substance by behind the stable supplying of liquid phase conveyance conduit 76, just can calculate the flow information of liquid phase fluid by the physical characteristic of Δ P and liquid phase fluid.

At some low pressure reactions, as the low pressure Fischer-Tropsch synthetic in, although pressure differential Δ P is very little, its also be this reaction can not bear, particularly big or when multistage reactor is arranged more when each stage reactor length, will cause whole pressure drop bigger, to the adverse influence that causes of reaction.In addition, owing to adjust pressure differential deltap P to keep liquid level 704 by liquid level inductor 706 and current-limiting apparatus 705.In the process of adjusting Δ P, just also might produce some influences, and then have influence on flowing of fluid in the first order reactor 71 pressure in the first order reactor 71.

Referring to shown in Figure 10, it is similar to embodiment shown in Figure 9.In the present embodiment, cancelled the current-limiting apparatus 705 that is arranged on the gas-phase transport pipeline 75.Owing to do not had the existence of current-limiting apparatus 705, just eliminated the pressure differential that produces owing to gas-phase transport pipeline 75.Simultaneously, be provided with a liquid pump 707 in liquid phase conveyance conduit 76 and carry liquid phase fluid, and can monitor the variation of liquid level 704 and its output signal is flowed to liquid pump 707 to keep liquid level 704 at a preposition by liquid level inductor 706, can guarantee the uniformity that liquid phase fluid flows like this.When the pressure on first order reactor 71 and the separator 703 was P1, the pressure of second level reactor 73 was P1 just also.Owing to do not had pressure differential on the gas-phase transport pipeline 75, adjust Δ P on the gas-phase transport pipeline 75 like that in order to keep liquid level 704 shown in also just needn't image pattern 9, thereby the pressure that has reduced in the reactor changes.Like this, just can eliminate under the situation that guarantee the liquid phase fluid steady flow, guarantee well carrying out of reaction in the pressure drop that reaches on the reactor between reactor.

In the present embodiment, described liquid pump 707 can be positive displacement pump (Positive displacement pump) or centrifugal pump (Centrifuge pump) etc., preferably uses positive displacement pump.Simultaneously, liquid pump 707 is preferably the function with measurement, so that the flow velocity of real-time detection liquid phase fluid.For liquid phase fluid is distributed in the second level reactor 73 uniformly, can in second level reactor 73, be provided with sprayer unit (not shown), be distributed in uniformly in the beds 74 thereby make after the liquid phase fluid of liquid phase conveyance conduit 76 conveyings enters first order reactor 73.In addition, in the present embodiment, also can be provided with check-valves (not shown) to prevent the liquid refluence in liquid phase conveyance conduit 76 in liquid pump 707 backs.

As seen, in an embodiment of the present invention, separate by heterogeneous effluent first order reactor 71, gaseous fluid and the interactional possibility of liquid phase fluid in course of conveying have been reduced, guaranteed continuity or uniformity in the material transmission, thereby multistage reactor just can better be simulated the performance of a beds of being made up of the beds of described multistage reactor.In addition, owing to separate, just can carry out sampling analysis to the component of effluent more accurately, thereby avoid traditional the heterogeneous fluid incomplete problem of sampling by 703 pairs of heterogeneous effluents of separator.

In some reactions, liquid phase fluid also is heterogeneous, and in synthesizing as Fischer-Tropsch, liquid phase fluid includes water and oil phase.At this moment, just may be provided with agitating device (not shown) in separator 703 has heterogeneous liquid phase fluid and stirs the uniformity of guaranteeing in the liquid phase fluid course of conveying fully to mix described.Described stirring can be adopted mechanical agitation, magnetic agitation etc.In a preferred embodiment, adopt the ultrasonic wave agitating device, this device can be installed on the position near separator 703 bottoms, and it can stir liquid phase fluid fully, reduces the interference of liquid level inductor 706 as much as possible and avoids because stirring increases the temperature of liquid phase fluid.

Shown in Fig. 9-10, compare with the temperature of first order reactor 71 exit effluents, when the temperature of separator 703 is high, enters in the liquid phase fluid in the separator 703 easily the component of volatilization and will volatilize and enter into gaseous fluid; When the temperature of separator 703 was hanged down, condensation just may take place and enter into liquid phase fluid in a part of gaseous fluid.No matter as seen the temperature of separator 703 is high or low, all can the component or the state of the effluent fluid of coupled first order reactor be exerted an influence.Like this, the next stage reactor receives between the fluid that fluid and upper level reactor exit discharge variation has taken place, thereby just can not guarantee continuity or the uniformity of fluid at transport process.In order to keep the stable of effluent component and state, the temperature that is preferably the described separator 703 of maintenance is identical with the temperature of described first order reactor 71 exit effluents, enters described separator 703 interior its states with regard to the effluent that guarantees first reactor as much as possible like this and does not change.

As shown in figure 11, with first order reactor 71 is example, for entering separator 703 back temperature, the effluent of better guaranteeing first order reactor 71 do not change, described first order reactor 71 and separator 703 are one-body molded, like this, separator 703 and first order reactor 71 are in the individual system, thereby can guarantee the unanimity of temperature, just the possibility of better having avoided component, state to change.

In embodiments of the present invention, described multistage piston flow reactor 707 also can be made up of three or more parallel to each other and reactors series connection.Described separator can be installed on the exit of each stage reactor, and itself and reactor are provided with separately respectively, even one-body molded setting, and can current-limiting apparatus is set on the gas-phase transport pipeline or the liquid pump is set on the liquid phase conveyance conduit according to different being reflected at.In addition, described a plurality of tandem reactor also can vertically be provided with.

Claims (23)

1. device that is used to develop commercial scale laminar flow Catalytic processes, it comprises the first laboratory scale combined multi-stage piston flow reactor, plurality of conduits, sampling valve and a temperature control equipment; The described first combined multi-stage piston flow reactor is the piston flow reactor of three grades of series connection at least, and each stage reactor all offers inlet, exports and be mounted with beds; Described plurality of conduits includes the fresh reactant material pipe that links to each other with the first order reactor inlet of the described first combined multi-stage piston flow reactor and is connected the outlet of continuous two-stage reactor and the conveyance conduit of inlet; Described sampling valve connects wherein, and the outlet of A reactor links to each other so that the effluent of respective reaction device is sampled with the inlet of next stage reactor or with the outlet of afterbody reactor; It is characterized in that: the every stage reactor in the described combined multi-stage piston flow reactor all can be arranged in the described temperature control equipment so that this combined multi-stage piston flow reactor has a common controlled temperature environment.

2. device as claimed in claim 1, it is characterized in that: described device also is provided with one or more laboratory scale combined multi-stage piston flow reactors in addition, and it has identical reactor progression and the same sampling valve that is provided with the described first combined multi-stage piston flow reactor; Each stage reactor in the combined multi-stage piston flow reactor of described other setting all offers entrance and exit; Described fresh reactant conduit also links to each other with the first order reactor inlet of the combined multi-stage piston flow reactor of described other setting; What in addition, the combined multi-stage piston flow reactor of described other setting was parallel with the described first combined multi-stage piston flow reactor is arranged in the described temperature control equipment so that whole combined multi-stage piston flow reactor has a common controlled temperature environment.

3. device as claimed in claim 2, it is characterized in that: described device also includes some first control valves, some second control valves and an external reactors; Described some first control valves link to each other with described fresh reactant conduit so that independent and quantitative input fresh reactant thing in each corresponding combined multi-stage reactor; Described external reactors offers inlet, exports and is mounted with catalyst, and the inlet of described external reactors also links to each other with described fresh reactant conduit; The outlet of described external reactors links to each other with each combined multi-stage reactor respectively by described some second control valves, the effluent of importing described external reactors in each combined multi-stage reactor of correspondence that equally can be independent and quantitative.

4. device as claimed in claim 1, it is characterized in that: described device also comprises a detection reaction device that offers inlet, exports and be mounted with a beds, links to each other with the outlet of described detection reaction device in order to sampling valve that its effluent is sampled and facility from selected material to the inlet of described detection reaction device that import; Simultaneously, the inlet of described detection reaction device also with the described first combined multi-stage reactor in the outlet of A reactor link to each other to receive the effluent of this stage reactor.

5. device as claimed in claim 4, it is characterized in that: described detection reaction device comprises fixed bed reactors.

6. device as claimed in claim 4, it is characterized in that: described detection reaction device comprises back-mix-flow reactor.

7. device as claimed in claim 4, it is characterized in that: described detection reaction device comprises the microresponse device array of a two dimension.

8. device as claimed in claim 4, it is characterized in that: described selected material comprises a selected amount of fresh reactant thing.

9. device as claimed in claim 4, it is characterized in that: described selected material is included in reaction product or the accessory substance that reacts and generated in the described combined multi-stage reactor.

10. device as claimed in claim 4 is characterized in that: the beds that loads in the described detection reaction device is identical with beds in the described combined multi-stage reactor.

11. a device as claimed in claim 10 is characterized in that: described selected material comprises the noxious material that can make the catalyst poisoning in the described combined multi-stage reactor.

12. a device as claimed in claim 4 is characterized in that: the catalyst that loads in the described detection reaction device is different with the catalyst in the described combined multi-stage reactor on physics or chemical property.

13. a device as claimed in claim 4 is characterized in that: described detection reaction device also is arranged in the described temperature control equipment.

14. device as claimed in claim 1, it is characterized in that: described device also comprises a multistage detection reaction device, this multistage detection reaction device is made up of the fixed bed reactors of a plurality of series connection, and wherein each reactor all offers inlet, exports and be mounted with beds; The inlet of a reactor in the multistage detection reaction device links to each other with the outlet of A reactor in the described first combined multi-stage reactor, in order to receive the effluent of this stage reactor; Described fresh reactant conduit links to each other with the first order reactor inlet of described multistage detection reaction device; Simultaneously, described device also includes and links to each other with the outlet of every stage reactor in the described multistage detection reaction device in order to the sampling valve that its effluent is sampled and the pipeline of a selected material of reactor inlet input in described detection reaction device.

15. a device as claimed in claim 14 is characterized in that: described multistage detection reaction device is arranged in the temperature control equipment identical with the described first combined multi-stage reactor.

16. device as claimed in claim 14, it is characterized in that: described multistage detection reaction device is arranged in the temperature control equipment different with the described first combined multi-stage reactor, has different heat environment to reach described detection reaction device with described combined multi-stage reactor.

17. a device as claimed in claim 1 is characterized in that: described sampling valve such as comprises at dynamic sampling valve.

18. a catalytic process exploitation apparatus as claimed in claim 1 is characterized in that: described conveyance conduit is provided with static mixer.

19. a device as claimed in claim 18 is characterized in that: after described sampling valve is arranged at described static mixer, be convenient to the fluid after stirring is sampled.

20. a device as claimed in claim 1 is characterized in that: described temperature control equipment comprises the fluidization sand-bath.

21. a device as claimed in claim 1 is characterized in that: described device also includes the pipeline of the selected material of input in the reactor that can select of other setting in the described first combined multi-stage reactor.

22. a device as claimed in claim 1 is characterized in that: described device also includes analytical equipment, described analytical equipment links to each other with corresponding sampling valve so that the effluent of the reactor of sampling valve collection is carried out sampling analysis.

23. a device as claimed in claim 1 is characterized in that: the beds in all every stage reactors can be loaded in the reactor simultaneously.

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