CN101274260A

CN101274260A - Catalytic hydrotreating nasty raw material investigation method

Info

Publication number: CN101274260A
Application number: CNA2007103075372A
Authority: CN
Inventors: 理查德·F·鲍曼
Original assignee: Accelergy Shanghai R & D Center Co Ltd
Current assignee: Accelergy Shanghai R & D Center Co Ltd
Priority date: 2006-12-29
Filing date: 2007-12-29
Publication date: 2008-10-01
Also published as: WO2008080365A1; US20100320121A1

Abstract

A method for hydroprocessing dirty feedstocks, comprises the steps of: feeding selected partial pressures of said feedstock and hydrogen to the inlet the first reactor stage of a first composite multi-stage series-connected laboratory scale plug flow reactor including at least three reactor stages, the catalyst beds of each of said reactor stages including catalyst particles capable of catalyzing the removal by hydrogen of heteroatoms from said heterocyclic molecules; sampling the effluents of each of said reactor stages; measuring the concentration of heterocyclic molecules in said dirty feedstock in the concentrations of heterocyclic molecules and intermediate and final products and by products of the catalytic reaction in the effluents of each of said reactor stages.

Description

The research method of the unclean raw material of a kind of catalytic hydrogenation treatment

[technical field]

The present invention relates to a kind of cost that can be lower, fast exploitation is a kind of is found to the commercial catalyst of using that is used for unclean raw material hydrotreatment (Hydroprocessing) and the research method of corresponding laminar flow Catalytic processes at first from it.

[background technology]

In order to amplify (Scale-up) a kind of laminar flow Catalytic processes that is used for unclean raw material hydrotreatment, just be necessary to study the influence of raw material components, reaction time (Time on Stream), reactant residence time (ResidenceTime), catalyst particle size, shape and its other features and temperature curve (Temperature Profile) to reaction rate and catalyst selectivity.In traditional amplification research, what the first step related to earlier usually is selecting catalyst and some intrinsic propestieses that determine selected catalyst.Pass influence in order to reduce matter to operating process, the operation of this step often be select through the crushing of dilution or powder catalyst under isothermy, carry out.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 raw material components, air speed, pressure and reactant residence time.Subsequently, 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.

In plant-scale trickle bed hydrotreatment (Hydrotreating) reactor, usually, the diameter of catalyst granules is 1.3-3.2mm, and its average length is 5-10mm.This scope inner catalyst size has just been reacted the abundant use that will reach on the one hand catalyst, keeps a kind of balance that obtains between pressure drop controlled in the reactor on the other hand again.To hydrodesulfurization (Hydrodesulphurization, HDS), in the size range of this catalyst granules, the diffusion retardance (diffusional resistance of sulphur compound in the catalyst hole) in the particle can significantly reduce the reaction rate of HDS; And the diffusion effect in the particle changes along with the difference of reaction condition (particularly temperature) and sulphur compound intrinsic reactivity.Diffusion in the research particle is very important for mechanism and the technology of overall understanding HDS.Yet, in disclosed document, much utilize the catalyst of full-scale industrial catalyst particle or crushing to study HDS at present although had about HDS, still there are not enough data relevant with the diffusion in the particle.

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 fixed bed reactors that do 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 big multi-catalyst, its reaction rate and relevant with the time that reactant residence time and reactor continue to react to product selectivity.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 materials such as hydrogen sulfide and ammonia and with its reaction in, the water oxidation that catalyst can be formed in the conversion process, cover layer and catalyst poisoning etc. be can form in its surface, thereby catalyst condition or specifications vary caused.In addition, because the reduction that surface-catalyzed reactions and accumulating in the hole thereof also can cause mass transfer rate (Mass Transfer Rate) takes place in reactant and product in catalyst pores.

The hydrotreatment of unclean raw material has comprised the step of a series of continuous its qualities of lifting.At first to carry out desulfurization, deoxidation and denitrogenation to remove heterocycle molecule (Heterocyclic Molecules) wherein and to follow Hydrodearomatization (Hydrodearomatization) to raw material to remove polynuclear armatic hydrocarbon.The catalyst that uses this moment must be typically and use well-known metal sulfide catalyst sulphur, oxygen and the immunity of nitrogen poisonous substance.Subsequently, raw material is carried out open loop operation, optionally the carbon-carbon bond in the ring structure being carried out open loop, and make some long-chain molecules be cleaved into short chain.Be typically this step and use metal sulfide catalyst equally, the content of over cure is not usually less than the sulfur content in the catalyst that uses in the previous step.Next, if necessary, can carry out hydrogenation again to raw material and make hydrocarbon key wherein saturated.The catalyst that uses in this step is typically molecular sieve carried a large amount of group VIII base metal type catalyst, certainly, also can use the noble metal type catalyst.At last, raw material is carried out hydrocracking and hydrocarbon and the cycloalkane of isomerization to obtain to expect that chain length distributes.The catalyst that uses in this step is typically molecular sieve carried group VIII noble metals type catalyst.Each step can be operated in independent piston flow reactor, certainly, in steps or wherein some can in piston flow reactor, carry out with vertical catalyst bed interval, wherein, be mounted with the catalyst of suitable this step in each catalyst section.

Although relatively disclosed unsupported catalyst and application thereof different in the hydrotreatment in the Duo patent, wherein only have only minority to be applied to commercial-scale non-supported hydrogenation and handle catalyst.This is with some is different according to a large amount of potential performance of proving in the laboratory.Load in existing refining process equipment that to have very highly active catalyst be fairly simple.Yet under many circumstances, its technology and equipment do not design at the heat radiation that active high catalyst brought and the consumption of hydrogen.Application need catalyst manufacturers and the concise factory close cooperation of such catalyst in commerce guaranteed to reach the performance of expectation and is unlikely to take place other influence of not expecting or operating difficulties.In addition, only comprise group VIII and VI family metal in the catalyst of non-loading type, price just becomes an important factor.Compare with loaded catalyst, the density of unsupported catalyst is higher, and metal concentration wherein is bigger, and like this, catalyst can significantly increase the cost that reactor is filled.Therefore, have in the hydrotreating catalyst market that to sell in a large number, only have only the limited hydrotreating catalyst that can be used in the commerce existing.Such as Nebula-1 in the Nebula catalyst family of Albemarle catalyst Co. and Nebula-20 all are catalyst of commercial level.As seen, still have very big chance to throw in the overall cost that other more advanced catalyst improves the quality of product and reduces hydrodesulfurization system clean fuel to market.

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.

Nowadays, combinatorial chemistry is used in pharmaceuticals industry widely, compared to before, it can synthesize, purifies and assess new drug at faster speed.In the pharmaceutical chemistry field, usually each medicine is only needed to test very in a small amount, have only those in associated biomolecule is measured, to have active medicine and just can amplify, so the reaction that is typically in the pharmaceutical chemistry field all is to carry out in scope relatively very in a small amount.The chemistry of this medicine that is used for manufacture scale amount is very different with the chemistry that is used in synthetic in a small amount.

Combinatorial chemistry also is applied in the petrochemistry, is used for finding the new catalytic material of use in different refinings are used.Yet, when considering industrialization, just must make the result that obtains in less laboratory scale with will between the result that commercial scale obtains, produce related.At present, a combinational chemistry that is used for confirming the useful catalysts used in differential responses is to place at least two kinds of catalyst on a metallic plate, uses gaseous reactant contacting metal plate then, and then confirms catalyst by the GC/MS assay products.This method has its limitation, at least concerning a large amount of heat release and endothermic catalytic reaction, be difficult to the result who obtains in result and the commercial scale from little quantitative response is associated, and this limitation partly is because the heat biography that obtains in little quantitative response can not reasonably cause with observed being associated in big reactor.The multiple nearest example of this combined method and the example that some are representative can announce the 5th, 776 with reference to United States Patent (USP), and No. 359, the 5th, 853, No. 356, the 5th, 939, No. 268, the 6th, 149, No. 882, the 6th, 790, No. 322 and the 7th, 025, No. 828.In addition, as United States Patent (USP) the 6th, 806, No. 087 described, and it has discussed the problem of process in amplifying to a certain extent, yet its enough concern of failing comprises that heat in the operation of commercial scale catalyst passes and the complete scale-up problem of matter biography effect.

In the endothermic reaction, it is most important that heat passes effect, such as the hydrotreatment such as hydrocracking, hydrodesulfurization and hydroisomerization etc. that is the endothermic reaction, heat biography and matter passed very sensitivity of effect.Because heat passes and matter passes the existence of effect, generate in the little quantitative response of acceptable product mixtures certain other unwanted secondary response of level may take place.Like this, be extrapolated on the industrial-scale reactor just very difficult from a small amount of endothermic reaction, obtain the result.It also is impossible using industrial-scale reactor to carry out the high flux combinatorial chemistry simultaneously.

So, need that exploitation is a kind of to be considered to produce anti-thing distributes and other answer heat in the characteristic to pass and matter passes effect combinatorial chemistry technique to find and assess the method for the catalyst system of optimum will be very useful in order to overcome the deficiencies in the prior art.

[summary of the invention]

The object of the invention provides the method for the preferable combination that is constituted between a kind of definite fast at lower cost structure of reactor, catalyst performance, beds structure and process conditions, and then the result amplified to be applied to unclean raw material is carried out on the commercial scale catalysis processing procedure and reactor assembly thereof of hydrotreatment, thereby target product has higher productive rate and selectivity.

So-called unclean raw material is meant such as the C from crude oil that includes big hetero atom molecule ¹⁰-C ²⁰⁺Cut and the circulation wet goods that in refining operation, produces.

The method that the present invention relates to relates to uses the laboratory scale catalytic process exploitation apparatus of high flux, wherein high flux laboratory scale catalytic process exploitation apparatus comprises the piston flow reactor (plug-flow reactor) of laboratory scale plural serial stage, independent but the continuous step mutually of each of the hydrotreatment of on unclean raw material, carrying out with circulating research, these steps include removes the heteroatom step, the saturated treatment step of many ring material keys, split carbon-carbon bond step in the ring molecule, the hydrocarbon molecules step that saturated unsaturated molecular link step and hydrocracking and isomerization obtain.In circulation each time, the composition of the product that produced in reactor by laboratory scale and character are taken a sample and characterize, and the test result of each circulation is with helping determine the character of catalyst bed in the next round circulation and the selection of process conditions, to improve selectivity and the productive rate in the hydroprocessing.

The process conditions of studying comprise not the relative dividing potential drop of reactant and product on the same group temperature, pressure, flow velocity and the laboratory scale reactor catalyst bed at different levels.Catalyst test comprises, under the different catalytic conditions and under the reaction time, the determining of the catalysis efficiency of catalyst, for example catalyst particle size, profile to it at the catalytic performance of the laboratory scale that connects continuously with the diverse location on the reactor.The catalytic bed Research on Architecture comprises the influence of the different framework beds that use in the laboratory scale reactor, and comprise change from a laboratory scale with reactor to next laboratory scale with the employed specificity of catalyst of reactor.

The data that generated by test result can be used for designing commercial scale Catalytic processes and the reactor assembly that unclean raw material is carried out hydrotreatment, so that catalyst performance and the operational factor used, for example the local pressure of reaction raw materials and product, temperature, pressure and flow velocity reach optimization.In the combined multi-stage series connection fixed bed reactors in embodiments of the present invention, just can be by each independent beds or catalyst bed interval being divided into the continuous fragment that longitudinally distributes, and then can study that dynamics, matter in the different chemical reaction that takes place in vertical fragment of each described beds or catalyst bed interval passes and heat passes characteristic.Like this, each that just can utilize that described laboratory scale combined multi-stage series connection fixed bed reactors study in the industrial-scale reactor unclean raw material of hydrotreatment promotes in the step of its quality, and the dynamics of the differential responses that take place in beds or catalyst bed interval, matter pass and heat passes the top rake of characteristic.According to the data that research institute obtains, develop the behavior that the forecasting type reactor model reflects commercial scale hydrorefining catalyst system by using laboratory-scale reactors.

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,, just can simulate many characteristics of industrially scalable reactor, thereby accelerate the process of industrially scalable by the test under the different test conditions.

[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.

Fig. 8 is the diagram that can be used for the Thiele modulus of definite a kind of catalyst.

Fig. 9 is the efficiency factor of employed catalyst among Fig. 8 and the graph of a relation of its Thiele modulus.

Figure 10 is respectively the catalyst of the crushing of using in the Fischer-Tropsch synthesis and with the efficiency factor of kind commercial size catalyst and the graph of a relation of conversion ratio.

Figure 11 is another device schematic diagram that piston flow reactor of the present invention is provided with.

Shown in Figure 12 be the device schematic diagram that is used to simulate the multistage piston flow reactor of isothermal of adiabatic reactor of the present invention.

Figure 13 is the schematic diagram of an embodiment of reactor of the present invention and separator assembling.

Figure 14 is the schematic diagram of another embodiment of reactor of the present invention and separator assembling.

Figure 15 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 reactor 17 and the outlet of reactor 17 be respectively arranged with

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 to combined multi-stage piston flow reactor 11.In addition, also can a sampling valve (not shown) be set 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 a 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 second embodiment of piston flow reactor 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

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.In addition, also a control sampling valve (not shown) can be set 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 link to each other with 59 with the

corresponding material source

55,57 of giving respectively.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, by gaseous state or the liquid input that provides in the third level reactor 41 of detection reaction device 35 is provided, 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 other form detection reaction device 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, and this detection reaction device 101 is the fixed bed reactors 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 is a laboratory scale 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, be input in the

reactor

39 and 41 in the corresponding detection reaction device 35 in order to selectable selected part effluent 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 corresponding material in

reactor

37,39 and 41 to all reactors in the detection reaction device 35,

reactor

beds

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 Proserv AS 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 standard 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 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.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 with the material of hydrocracking catalyst reaction, 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 many group VIII catalyst surfaces, thereby reduces the surface that hydrogen can be used, and becomes a factor of restriction hydrogen reaction speed.The performance of corresponding reactor in concentration ratio by hydrogen and carbon monoxide (or carbon dioxide) in the raw material of adjusting input in selected

detection reaction device

35 and 101 and more described detection reaction device and the multistage reactor 11, 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 piston flow reactor heavy oil concentrate and conversion process in the water that increases reaction rate is had positive effect.By add quantitative water or other oxygen-containing molecules 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.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 547,579,553 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 piston flow 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.

In the combined multi-stage series connection fixed bed reactors in embodiments of the present invention, it can be by being divided into continuous vertical fragment to each independent beds or catalyst bed interval, and then can study that dynamics, matter in the different chemical reaction that takes place in vertical fragment of each described beds or catalyst bed interval passes and heat passes characteristic.Like this, each that just can utilize that described combined multi-stage series connection fixed bed reactors study at the unclean raw material of hydrotreatment promotes in the step of its quality, and the dynamics of the differential responses that take place in beds or catalyst bed interval, matter pass and heat passes the top rake of characteristic.In the step that begins to remove oxygen, sulphur and nitrogen heteroatom in the heterocycle molecule, unclean raw material and hydrogen are input in the first order reactor in first combined multi-stage series connection piston flow reactor, in the beds of this combined multi-stage piston flow reactor, include a kind of catalyst, representative is metal sulfide catalyst, thus its can the unclean raw material of catalysis and the reaction of hydrogen remove the hetero atom in the heterocycle molecule in the raw material.Initial intermediate ethanol (Alcohols), mercaptan (Thiols) and the amine (Amines) of generating earlier of catalytic action in this first combined multi-stage tandem reactor, these intermediates are separately converted to water, hydrogen sulfide and the ammonia of highly volatile under the reaction temperature condition more then, thereby remove from system in the gaseous state mode.When these intermediates under reaction condition were not transformed fully, they will be retained in and make catalyst poisoning in the system and cause puzzlement for follow-up step.By the beds of processing heterocycle molecule being divided into a series of three or more the vertical beds segments that are loaded into respectively in the reactor independently, and to the sample amount of reactant in the effluent of determining every stage reactor, intermediate and end product of the effluent of every stage reactor, like this, just can determine hetero atom is removed in the heterocycle molecule degree and the intermediate, end product and the accessory substance that in each stage reactor, generate, and then optimize process conditions and in system, do not have intermediate to leave over to guarantee intermediate to be converted into volatile products entirely.Can adopt gas phase or high pressure liquid chromatograph connexus spectrometer to analyze to the analysis of effluent.In addition, can use the pulse flame photometric detector to detect the existence of sulphur, (O17 Nuclear Magnetic Resonance O17NMR) detects oxygen and use chemoluminescence method (Chemiluminescence techniques) detects nitrogen to use GC/MS or oxygen 17 nuclear magnetic resonance apparatus.

Similar, each follow-up step hydrotreating step all carries out in continuous combined multi-stage series connection fixed bed reactors, and each combined multi-stage tandem reactor is three grades or multistage reactor.Simultaneously, effluent and hydrogen that follow-up each continuous step hydrotreating step all relates to previous step the afterbody reactor of the combined multi-stage reactor in rapid are input in the first order reactor of the combined multi-stage reactor in the next step, and measure the product in the effluent of each stage reactor of the concentration of the raw material in the combined multi-stage reactor that is input in the described next step and the combined multi-stage reactor in the described next step and the concentration of accessory substance.Carry out segmentation by beds to the unclean raw material of hydrotreatment, and the concentration of different component in each stage reactor effluent of sampling analysis, so just can use above-mentioned mini-plant to set up a model that is used to optimize each hydrotreating step operating condition, the performance of the commercial scale hydrorefining catalyst system that utilizes this model just can analyze to be used for the unclean raw material of hydrotreatment.

Using the hydrotreatment polynuclear armatic hydrocarbon to make in its saturated step, can be by the effluent of wherein each stage reactor being sampled and utilizing high-resolution phosphorus nuclear magnetic resonance apparatus (High-resolution P-NMR) or carbon-13 magnetic resonance instrument (C13 Nuclear Magnetic Resonance C13NMR) measures to study the technology of catalytic reaction in each stage reactor.For the Catalytic processes in split carbon-carbon bond and the isomerization steps, can use gas chromatograph the effluent measurement of relevant reactor to be studied in conjunction with high-resolution mass spectrometer (High-resolution Mass Spectroscopy) or high-resolution carbon-13 magnetic resonance instrument.In addition, also can use GC/MS to distinguish and measure different hydrocarbons.

In embodiments of the present invention, can also study behind initial heterocycle molecule treatment step, hetero atom in a small amount is to the influence of catalyst reactor function, and this can be by studying such as detection reaction device described in use Fig. 2-4 or 6.

According to the data that research institute obtains, develop the behavior that the forecasting type reactor model reflects commercial scale hydrorefining catalyst system by using mini-reactor.

Dynamics

Up to now, only be to be undertaken to the kinetic measurement of a piston flow reactor 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.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 relevant, just be necessary such as each the continuous vertical section inlet of beds of analyzing every standard liters in standard temperature and pressure (STP) (STP) down and the material fluid and the component in exit with the lengthwise position of beds.Like this, just can determine the kinetics of each effective section of a complete commercial scale system, when speed constant is straight line with respect to the curve of the distance of distance beds porch, show length along beds, the integration dynamics of system is constant; When slope of a curve constantly changes, show and variation has taken place apart from the relevant dynamics of the distance of porch (also may be the state of catalyst).

When the dynamics 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 (Regression Analysis) 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 (GraphicalMethods for Data 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%.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.

The dynamics of deep desulfuration is arranged by the hydrogenation treatment degree that direct sulphur extracts degree that desulfurization that (direct sulfur extraction) carry out handles or the sulphur sulfur-containing molecules before extracting.Wherein the direct desulfurization mode mainly can be owing to hydrogen sulfide be suppressed, and the hydrogenation treatment mode can be suppressed by nitrogen-containing compound.The different manifestations of the more known catalyst of industry on this dual mode, this is very important to the amount of the needed whole hydrogen of sulfur-bearing raw material that are used to handle known quantity undoubtedly.Like this, the dynamic (dynamical) understood in detail of deep desulfuration be can be used for selecting optimal catalyst at known demand; And under the situation of considering input, hydrogen cost and product quality, assessment is to the getable relative advantage of revision of grass-roots unit.

Since the reduction step by step of the sulfur content of stipulating in gasoline product and the diesel oil, and the sulfur content in the crude oil is more and more higher, and the problem of deep desulfuration becomes more and more important.One about the data survey of sulfur content and API degree in the vicennial crude oil of past show the raw material of U.S.'s refining crude oil continue towards sulfur content high direction develop.The thing followed promptly is that demand novel and that have more the deep desulfurization catalyst of usefulness is increased greatly, and the method that the present invention relates to can make the exploitation of this kind catalyst have more actual effect, and cost is lower, and efficient is higher.

Quality is transmitted

Usually, piston flow reactor of typical research is that the conversion ratio in the reactor of the reactor of the tiny catalyst by relatively being mounted with crushing under one group of given operating condition and the catalyst that is mounted with commercial size is finished with respect to the characteristics of the time of staying as the method for the matter transfer performance in the fixed bed reactors Catalytic processes.The particle of the catalyst of described crushing is often selected very little particle size for use, is preferably the catalyst granules of selecting the minimum dimension that can obtain for use, and certainly, prerequisite is that it still keeps its catalytic performance.The minimum dimension of catalyst granules depends on the performance of employed catalyst, and this minimum dimension can be determined by a simple experiment.In addition, the method that one simpler determines the matter transfer performance is exactly that the tiny catalyst of supposition crushing does not exist any matter to pass retardance, catalyst by relatively crushing and the conversion ratio in the catalyst of commercial size just can access matter and pass the information that blocks with respect to the difference of the characteristics of the time of staying so.For the reaction of a given raw material, carry out the numerical value that sampling analysis just can access conversion ratio by effluent to described two reactors.In addition, the flow velocity that offers the input of described two reactors also is adjustable, is input to the flow velocity of the input in the reactor that is mounted with the commercial size catalyst such as the flow velocity that can improve the input in the reactor that is input to the catalyst that is mounted with crushing or reduction.Like this, can have identical conversion ratio by making two reactors, the matter of the difference of the time of staying in just can reaction industry specification catalyst passes and has blocked so.

In addition, Hougen and Watson have disclosed a kind of strict more and very accurate technically method that is used for the matter transfer performance of definite commercial size catalyst by the third part " dynamics and catalyst " (Kinetics andCatalysts) of Wiley in " chemical technology principle " (Chemical Process Principles) of in March, 1966 publication in the 998-1000 page or leaf.Described method does not suppose that or not is zero that the matter of the tiny catalyst of crushing passes retardance, its earlier the ratio of the size of the ratio by the macroreaction speed in crushing catalyst and the commercial size catalyst and catalyst granules determine the Thiele modulus of this commercial size catalyst, and then determine the efficiency factor of commercial size catalyst by the graph of a relation of its efficiency factor and Thiele modulus.

The effectiveness of the hydrodesulfurization of model compound such as dibenzothiophen compound can be by change average particle size and detect the activity that this change adds catalysis and optionally combined influence is next determines experimentally in the diffusion couple light cycle oil in the particle.Under similar operating condition, the catalyst of full-size with and the crushing catalyst the effectiveness factor can determine.For the industrial catalyst of full-size,, cause the desulphurization reaction speed of dibenzothiophens all in the raw material and relevant sulfur-bearing reactant is reduced because of the diffusional resistance in the particle may be very big.Rendeing a service the factor is a good index weighing the material Transfer degree in the particle.For obtaining required performance, the numerical value of rendeing a service the factor needs more than or equal to 0.3, preferably between 0.8 to 0.9.The effectiveness of determining the material Transfer resistance in the sulfur-bearing reactant particle also is very important, it is relevant with the geometrical performance of sulfur-bearing reactant that the particle endoplasm passes retardance, and the influence that matter passes retardance can have various substituent typical sulfur fluorene compounds (DBT) acquisitions that increase molecular dimension by use.

Yet described method does not all provide any information about vertically changing along beds matter transfer performance, and its all be usually supposition in beds everywhere the matter transfer performance all be identical.This supposition all is incorrect in a lot of catalysis systems.Like this, owing to can not determine vertical variation of the matter transfer performance of beds in the fixed bed reactors, just can not be optimized it along beds.

In an embodiment of the present invention, by the beds in the piston flow reactor longitudinally being divided into the catalyst bed interval of at least three series connection, and then the effluent of each catalyst bed interval being carried out sampling analysis determine each vertically conversion ratio of section.Continuation is referring to shown in Figure 2, and

multistage reactor

11 and 35 all can comprise three or more single-stage reactors, is provided with the employing valve in the exit of every stage reactor, in order to measure the composition of every stage reactor effluent.

Multistage reactor

11 and 35 is arranged in the common temperature control equipment 33 to keep identical temperature environment, and simultaneously, it can receive the identical reactant input from reactant source 31.When carrying out basic matter biography research, temporarily can for

material source

55,57 and 59.Reactor 13 in the multistage reactor 11; beds 19 in 15 and 17; be tiny catalyst granules or pulverous catalyst granules of crushing in 21 and 23, and wherein be mixed with abundant inertia dilution particle be used for guaranteeing that multistage reactor 11 operates under isothermy through screening.

Reactor 37 in multistage reactor 35, beds 43 in 39 and 41, be the catalyst granules of commercial size in 45 and 47, it dilutes to guarantee that reactor 35 also can operate under isothermy through inertia dilution particle equally, and only dilution ratio is less.In order to study the matter transfer performance relevant of commercial size catalyst, set described

multistage reactor

11 and 35 and receive identical reactant input, and pressure and raw material flow rate all are consistent from reactant source 31 with longitude.Under a given group reaction condition, multistage reactor 11 just can and be determined in the different amount of every stage reactor entrance and exit place reactant feed by flow velocity with conversion ratio and the relation of the time of staying in every stage reactor of 35.

In the mensuration matter transmission method of a simplification, the ratio of the macroreaction speed of the catalyst of congener crushing is determined the efficiency factor of the commercial size catalyst in every stage reactor in the described multistage reactor 35 in the macroreaction speed by commercial size catalyst in every stage reactor of multistage reactor 35 and the respective reaction device of multistage reactor 11.For multistage reactor 11 and 35, constantly conversion ratio and the product that constantly generates and the accessory substance and the time of staying mapping of the reactant of accumulation of exit to its every stage reactor, and diagram and the data that obtain are matched, like this, just can obtain corresponding multistage reactor 11 or 35 macroreaction speed Ko (conversion ratio of the unit time of staying) by gained at the product of any time of staying correspondence or the illustrated slope of conversion ratio.Concrete drafting method can be referring to John M.Chambers, " the data analysis drafting method " of Chapman and Hall (Graphical Methods for Data Analysis), May nineteen eighty-three, ISBN:0412052717.When matter passes when unrestricted, macroreaction speed Ko just is not subjected to the constraint of catalyst granules diameter.By respectively to the macroreaction speed Ko of the reactor in multistage reactor 11 and 35 with corresponding conversion ratio mapping and compare, just can determine in the composite catalyst bed of multistage reactor 35 pass through the catalyst hole time matter biography limited longitudinal region.A kind of efficiency factor of catalyst equals the macroreaction speed Ko of this catalyst and the ratio of its intrinsic reaction rate Ki in a reactor.In the method for simplifying, often think that the catalyst of crushing passes retardance without any matter, so its macroreaction speed Ko just is considered to the intrinsic reaction rate Ki of this catalyst.Like this, on the optional position of the composite catalyst bed in multistage reactor 35, the ratio of the macroreaction speed Ko of the macroreaction speed Ko that the efficiency factor of described commercial size catalyst just equals at this commercial size catalyst on this position and the catalyst of the crushing on the relevant position.

When using the method for Hougen and Watson, just think that macroreaction speed Ko and its intrinsic reaction rate Ki of catalyst of crushing is inequality.Utilize diagram shown in Figure 8, can determine the Thiele modulus of optional position in the commercial size beds according to this method, this Thiele modulus is by determining at the ratio of the macroreaction speed of the catalyst of the crushing of the commercial size catalyst of this position and relevant position and the ratio of particle diameter thereof.Such as, in Fig. 8, when the particle diameter ratio of the catalyst of described crushing and described commercial size catalyst is 0.2 and the ratio of the macroreaction speed Ko of the catalyst of commercial size catalyst and crushing when being 0.34, be approximately 9 at the Thiele of this position catalyst modulus so.At this moment, referring again to shown in Figure 9, the beds of the commercial size in the reactor 35 so, the efficiency factor in this position approximately just is 0.27.In the running of multistage reactor 11 and 35, can carry out replication to efficiency factor relevant in the commercial size beds with longitude, so just can determine the influence of reaction time to the matter transfer performance of laminar flow catalysis system.Certainly, also can under different temperature and pressure conditions, measure, thereby determine the influence of the change of these parameters matter biography in the composite catalyst bed in the reactor 35.

Because efficiency factor is the ratio of catalyst macroreaction speed Ko and its intrinsic reaction rate Ki, so along beds a given lengthwise position, just can extrapolate its intrinsic reaction rate Ki by catalyst in the efficiency factor of this position and its macroreaction speed Ko.No matter the catalyst for crushing still is the catalyst of commercial size, its intrinsic reaction rate Ki is identical, so along the bed of commercial size catalyst, the efficiency factor of its optional position just can be determined by macroreaction speed Ko and the intrinsic reaction rate Ki of catalyst in this position of commercial size.

For a reaction, may there be different response paths in lengthwise positions different in the piston flow reactor beds, generate methane such as the conversion of sulfur-bearing or nitrogen raw material, carburizing or by hydrogenesis.Interval and matter passes the generation that matter in interval and the compartment system passes effect and kinetic effect for dynamics relevant with longitude in the system of probing into, so generation is present in the system and characterizes just very important along the behavior in the different dynamic ways for education footpath of the product of composite catalyst bed varied in thickness and accessory substance.After described interval is understood, with regard to can study one group given and to the system under the operating condition that has optimum balance with regard to the specific catalyst in generate the matter transfer performance of product by reactant.

As shown in figure 10, present embodiment provides the example of optimizing the vertical characteristics of beds in the fixed bed reactors.In Figure 10, its disclosed have be mounted with under common reactant feed and the one group of given temperature and pressure condition crushing and with the typical relation figure of the fischer-tropsch synthetic catalyst of kind commercial size efficiency factor and conversion ratio in fixed bed reactors.As shown in figure 10, reach in that part of beds of about 50-60% at conversion ratio, its quality transmission retardance is obviously to exist; Conversion ratio be greater than 70% beds in, its quality transmission retardance has not just existed.As seen, the beds that is formed by the commercial size catalyst granules has bigger matter and passes retardance when less efficiency factor, and this bigger matter passes retardance and can reflect along the difference on the thickness response path of the beds of the beds of crushing and commercial size.Simultaneously, bigger matter passes retardance and shows at the lower that part of beds of conversion ratio, as there is material the porch that contacts the beds of complete fresh feed, accumulates in the catalyst hole as wax.But this situation has not just existed at the lower position of the higher beds of conversion ratio.

In hydrotreating reactor, efficiency factor tends to when low cause producing a large amount of unwanted methane or form carbon coating.Specifically for the Fischer-Tropsch synthesis device that is mounted with the commercial size beds, the top of beds can produce the methane of substantial amount.This has caused the diffusivity of reactant gas in the catalyst hole very low, does not just transfer to generate a large amount of methane thereby the activity of such catalysts position reaches enough reactant gas.In order to optimize beds structure in the fixed bed reactors to avoid generating a large amount of unwanted methane in the porch of beds, just, so just can produce less methane such as using active lower catalyst in the porch of beds.

Crushing and catalyst granules commercial size that has different size except use is studied the matter transfer performance of beds in the fixed bed reactors, also can use the particle of different amount catalyst of containing of same size to study.Described particle is made up of as aluminium oxide or silica tiny or the powder catalyst and the inertia dilution of crushing.Powdered or tiny catalyst evenly mixes with tiny crushing inertia dilution and carries out sintering to form the particle of certain size.At this moment, the particle that just can select to have the lower content catalyst makes it be equivalent to the catalyst of the crushing described in the said method, the particulate that selection has the high level catalyst makes its catalyst that is equivalent to commercial size, and the selection of this content depends on the essence of activity of such catalysts and reaction.

Reactor is carried out in the commercial scale amplification process, and way is the matter transfer performance that checking obtains under isothermy in an adiabatic reactor preferably.In adiabatic reactor, the amount of the inertia dilution that is mixed with in the commercial size catalyst just needs less, and will control the diameter of heat pipe so that the heat performance of this adiabatic reactor can reflect the heat performance of the industrial-scale reactor of expection.

When the matter of research hydrotreating reactor passes effect, except reaction rate was mapped with respect to conversion ratio or the time of staying, also can map to the selectivity and the conversion ratio of methane.When the retardance of matter biography existed, the selectivity of methane was just very high.With the typical relation between the conversion ratio of the selectivity of methane in the synthetic fixed bed reactors of the Fischer-Tropsch of the stable state that is mounted with high activated catalyst and carbon monoxide is example (not shown).In this reactor, matter passes retardance and is maximized optionally influencing.For bigger that part of of the selectivity difference of methane, it is exactly to influence that matter passes for the catalyst of commercial size catalyst and crushing in the reactor.In the beds of conversion ratio at 35-80% of carbon monoxide, its selectivity to methane is all very little, and in this zone, it is just very little that matter passes the effect that influences.The conversion ratio of carbon monoxide greater than 80% beds in, for the catalyst of commercial size catalyst and crushing, it is very fast that the selectivity of methane all increases, and reaction rate also reduces, at this moment, meaning has other factors, but not matter passes the selectivity that is limiting activity of such catalysts and increasing methane.

Heat transmits

In piston flow reactor, most important concerning increasing reactor productivity to the understanding of its heat transfer property energy.In exothermic reaction, in Fischer-Tropsch synthesis, the reaction rate during high temperature is very high, yet, danger out of control is just arranged when temperature is too high.Temperature in the piston flow reactor in the beds can constantly change along the vertical and horizontal of beds, concerning the endothermic reaction that takes place in it, just need heat to avoid the generation of beds cold spot or reactor shutdowns reactor.

Device shown in Figure 2 can be used for studying the heat transfer property energy of piston flow reactor system, wherein, reactor 13 in the multistage reactor 11, be mounted with catalyst granules in 15 and 17 through the crushing of inert particle dilution, be mounted with catalyst granules in the reactor 37,39 and 41 in the multistage reactor 35 through inert particle dilution full-size.Thereby reactor 11 and 35 can be operated under isothermy by the ratio of adjusting inertia dilution particle and catalyst granules.Sampling valve 25,27,29,49,51 and 53 sample to the effluent of corresponding reactor respectively.In addition, the beds of each single-stage reactor in described multistage reactor 11 and 35 vertically, position and outer periphery are equipped with the temperature that thermocouple is measured beds therebetween.In addition, the diameter that thicker thermal conducting sleeve (Conductive Sleeves) reduces beds accordingly can be set in reactor, and then reduce reaction heat that the beds middle part produces and arrive by reactor wall and surround the path of the formed radiator of temperature control equipment (Heat Sink) of reactor wall, so just can study horizontal heat and pass effect (Lateral Heat Transfer Effects), certainly, compare with it, also can use continuous thin thermal conducting sleeve to increase the diameter of beds, can not well remove by reactor wall from the mid portion of beds up to reaction heat.

In the present embodiment, be preferably in different reactor flow velocity, pressure and productive rate and reaction beginning and course of reaction temperature and product are carried out retest.In addition, utilize method of the present invention, the catalyst granules that also can study different size and shape in the beds transmits performance and other technological parameters to heat, as to conversion ratio, selectivity and effect of kinetics.Like this, by the acquisition measurement data, just can probing into heat, to pass characteristic be the performance that how to influence reactor in whole multivariate space, the described multivariate space characteristics that plant-scale reactor had just.

As shown in figure 11, use the device of present embodiment can study matter biography relevant in the piston flow reactor, heat biography and dynamics equally with longitude.In the present embodiment, comprise a laboratory scale piston flow reactor 201, in the present embodiment, it is for fixed bed reactors and be mounted with the beds of being made up of the catalyst granules of commercial size 203 in it.Fresh material can be imported in reactor 201 in a fresh reactant thing source 205.Simultaneously, to 209-n, what the effluent of reactor 201 can be quantitative is imported into corresponding laboratory scale fixed bed reactors 207-1 in 207-n by control control valve 209-1.Reactor 207-1 is mounted with respectively in the 207-n corresponding more shallow has beds 211-1 than low-conversion to 211-n, and it dilutes so that these beds are operated under isothermy by abundant inert particle.In addition, to 213-n, reactant source 205 also can provide quantitative fresh material to arrive corresponding reactor 207-1 to 207-n by control control valve 213-1.Reactor 207-1 can sample to it to 215-n by corresponding sampling valve 215-1 to the effluent of 207-n.

When reactor 201 when set conversion ratio is operated under as 80% condition, can adjust the effluent that is input to the reactor 201 of reactor 207-1 in the 207-n to 209-n and 213-1 to 213-n and from the ratio between the fresh reactant thing in fresh reactant thing source 205 by control control valve 209-1, and then can adjust the conversion ratio of reactor 207-1 to 207-n, it is between 0 to 80%.With reactor 207-1 is example, control control valve 209-1 and 213-1 only make the effluent of reactor 201 enter among the reactor 207-1, and the thickness of control beds 211-1 transforms about 5% the effluent that enters the reactor 201 among the reactor 207-1 in reactor 201 again.Like this, beds 211-1 just is equivalent to a section (Cross-sectional Slice) of the piston flow reactor catalyst layer of conversion ratio between 80-85%.Similarly, control valve 209-2 and 213-2 make the material that enters reactor 207-2 have 40% conversion ratio, and the thickness of control catalyst layer 211-2 makes this material transform about 5% again, like this, catalyst layer 211-2 just can be used for simulating a section of the catalyst layer of conversion ratio between 40-45%.And then catalyst layer 211-1 just can be used to simulate the performance of a piston flow reactor along any lengthwise position section of catalyst layer to 211-n.

Catalyst layer 211-1 can have different components to 211-n, such as, catalyst layer 211-1 and 211-2 are mounted with the catalyst granules of crushing and the catalyst granules of commercial size respectively, and the dilution particle that all is mounted with inertia in two catalyst layers is operated in isothermy in order to guarantee catalyst layer.The matter that so just can measure any lengthwise position section of catalyst layer passes, heat passes and dynamics.Certainly, for different application, catalyst layer 211-1 can be mounted with the catalyst granules with different chemical or physics to 211-n.Enter reactor 207-1 thermal loss or its temperature in the 207-n process for fear of the effluent of reactor 201 and raise, often be coated with insulating materials to avoid above-mentioned situation on pipeline in coupled reaction device 201 and 207-1 to 207-n and the control valve.In addition, can to 207-n common temperature control equipment 217 be set to reactor 201 and reactor 207-1 and control its temperature, perhaps for different demands, reactor 201 and reactor 207-1 also can be provided with independently temperature control equipment respectively to 207-n.In addition, the fresh reactant thing of reactant source 205 often need heat before 207-n at supply response device 207-1.Mode of heating can adopt the known direct mode of heating of industry that reactant is heated, as sand-bath heater coil (Heating Coil in a Fluidized Sand Bath) or infrared heating furnace etc., so that the catalyst layer at reactor inlet place reaches suitable temperature conditions.

According to different goals of the invention, as amplification or other purposes etc., as Fig. 2,4, reaction unit of the present invention shown in 7 and 12 can be used to detect the operational factor of piston flow reactor under various objectives, such as, under the condition of different reaction temperatures, pressure, catalyst shape and size, detect the activity and the matter that are associated with longitude and pass the characteristic 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 process.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 12, 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 13, 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 13, 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 13, 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 14, it is similar to embodiment shown in Figure 13.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 13, 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 Figure 13-14, 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 15, 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

1. a research is used for the method for operational factor of the unclean raw material of hydrotreatment of commercial scale laminar flow Catalytic processes and reactor assembly, and it comprises:

A) the first laboratory scale combined multi-stage series connection piston flow reactor is set, it is at least three grades of tandem reactors, and unclean raw material with selected dividing potential drop and hydrogen are imported to remove the hetero atom in the heterocycle molecule in the described unclean raw material in the porch of the first order reactor in the described first combined multi-stage reactor in it; Beds in each stage reactor of the described first combined multi-stage reactor comprises and can catalysis removes heteroatomic catalyst granules in the described heterocycle molecule by hydrogen, described to remove the hetero atom in the heterocycle molecule in the unclean raw material be to carry out under the operating condition of selected one group of temperature, pressure, reactant flow velocity and product flow velocity, and the catalyst in the beds in the described laboratory scale reactor has optional features;

B) effluent of each stage reactor in the described combined multi-stage reactor is sampled;

C) measure the concentration of heterocycle molecule, intermediate, end product and accessory substance in the concentration of heterocycle molecule in the described unclean raw material and each the stage reactor effluent;

D) at repeating step under the selected different described operating condition and/or under selected different specificity of catalyst a) to c);

E) utilization removes the result who measures gained in the operation at a hetero atom and is chosen in characteristic and productive rate and the selectivity of operational factor to improve described laboratory scale piston flow reactor that follow-up hetero atom removes the beds in the operation.

2. the method for claim 1 is characterized in that: comprise in the described measurement and measure mercaptan, amine and alcohol in each stage reactor effluent.

3. the method for claim 1 is characterized in that: described method also comprises,

F) the second laboratory scale combined multi-stage series connection piston flow reactor is set, effluent and the hydrogen from the afterbody reactor of described first multistage reactor with selected dividing potential drop is imported in the porch of the first order reactor in described second multistage reactor in it, so that the polynuclear aromatic hydrocarbon molecule in the described effluent is saturated; Beds in each stage reactor of the described second combined multi-stage reactor comprises the saturated catalyst granules of polynuclear aromatic hydrocarbon molecule in the effluent that can catalysis makes by hydrogen in the first order reactor that is input to described second multistage reactor; Described to make the saturated operation of polynuclear aromatic hydrocarbon molecule in the effluent be to carry out under the operating condition of selected one group of temperature, pressure, reactant flow velocity and product flow velocity, and the catalyst in the beds in the described second laboratory scale reactor has optional features;

G) effluent of each stage reactor of described second multistage reactor is sampled;

H) product that generates by catalytic reaction in the effluent of each stage reactor of described second multistage reactor of measurement and the concentration of accessory substance;

I) at repeating step f under the selected different described operating condition and/or under selected different specificity of catalyst) to h); With

J) utilize the result who in a polynuclear aromatic hydrocarbon molecule operated in saturation, measures gained to be chosen in the characteristic and productive rate and the selectivity of operational factor of the beds in the follow-up polynuclear aromatic hydrocarbon molecule operated in saturation to improve the described second laboratory scale piston flow reactor.

4. method as claimed in claim 3 is characterized in that: described method also comprises,

K) the 3rd laboratory scale combined multi-stage series connection piston flow reactor is set, effluent and the hydrogen from the afterbody reactor of described second multistage reactor with selected dividing potential drop is imported in the porch of the first order reactor in described the 3rd multistage reactor in it, so that disconnect from the carbon-carbon bond in the ring molecule in the effluent of described second multistage reactor; Beds in each stage reactor of described the 3rd combined multi-stage reactor comprises the catalyst granules that the carbon-carbon bond of the ring molecule in the effluent that can catalysis makes by hydrogen in the first order reactor that is input to described the 3rd multistage reactor disconnects; The described operation that carbon-carbon bond in the effluent is disconnected is to carry out under the operating condition of selected one group of temperature, pressure, reactant flow velocity and product flow velocity, and the catalyst in the beds in described the 3rd laboratory scale reactor has optional features;

L) effluent of each stage reactor of described the 3rd multistage reactor is sampled;

M) product that generates by catalytic reaction in the effluent of each stage reactor of described the 3rd multistage reactor of measurement and the concentration of accessory substance;

N) at repeating step k under the selected different described operating condition and/or under selected different specificity of catalyst) to m); With

O) utilize the result who in the operation that carbon-carbon bond disconnects, measures gained to be chosen in the characteristic and productive rate and the selectivity of operational factor of the beds in the operation that follow-up carbon-carbon bond disconnects to improve described the 3rd laboratory scale piston flow reactor.

5. method as claimed in claim 4 is characterized in that: described method also comprises,

P) the 4th laboratory scale combined multi-stage series connection piston flow reactor is set, effluent and the hydrogen from the afterbody reactor of described the 3rd multistage reactor with selected dividing potential drop is imported in the porch of the first order reactor in described the 4th multistage reactor in it, so that hydrocarbon molecules hydrocracking and isomerization in the effluent of described the 3rd multistage reactor; Beds in each stage reactor of described the 4th combined multi-stage reactor comprises hydrocarbon molecules hydrocracking and the isomerized catalyst granules in the effluent that can catalysis makes by hydrogen in the first order reactor that is input to described the 3rd multistage reactor; Describedly make that the hydrocracking of hydrogen compound molecule and isomerized operation are to carry out in the effluent under the operating condition of selected one group of temperature, pressure, reactant flow velocity and product flow velocity, the catalyst in the beds in described the 4th laboratory scale reactor has optional features;

Q) effluent of each stage reactor of described the 4th multistage reactor is sampled;

R) product that generates by catalytic reaction in the effluent of each stage reactor of described the 4th multistage reactor of measurement and the concentration of accessory substance;

S) at repeating step p under the selected different described operating condition and/or under selected different specificity of catalyst) to r); With

T) utilize the result who in hydrocracking and isomerized operation, measures gained to be chosen in the characteristic and productive rate and the selectivity of operational factor of the beds in follow-up hydrogenation cracking and the isomerized operation to improve described the 4th laboratory scale piston flow reactor.

6. method as claimed in claim 4 is characterized in that: described method also comprises,

U) the 4th laboratory scale combined multi-stage series connection piston flow reactor is set, effluent and the hydrogen from the afterbody reactor of described the 3rd multistage reactor with selected dividing potential drop is imported in the porch of the first order reactor in described the 4th multistage reactor in it, so that the unsaturated molecule in the effluent in the first order reactor is saturated; Beds in each stage reactor of described the 4th combined multi-stage reactor comprises the saturated catalyst granules of unsaturated molecule in the effluent that can catalysis makes by hydrogen in the first order reactor that is input to described the 3rd multistage reactor; Described to make unsaturated molecule is saturated in the effluent operation be to carry out under the operating condition of selected one group of temperature, pressure, reactant flow velocity and product flow velocity, and the catalyst in the beds in described the 4th laboratory scale reactor has optional features;

V) the effluent of each stage reactor of described the 4th multistage reactor is sampled;

W) product that generates by catalytic reaction in the effluent of each stage reactor of described the 4th multistage reactor of measurement and the concentration of accessory substance;

X) at repeating step u under the selected different described operating condition and/or under selected different specificity of catalyst) to w); With

Y) utilize the result who in the operation that once unsaturated molecule is saturated, measures gained to be chosen in the characteristic and productive rate and the selectivity of operational factor of the beds in the saturated operation of follow-up unsaturated molecule to improve described the 4th laboratory scale piston flow reactor.

7. method as claimed in claim 6 is characterized in that: described method also comprises,

Z) the 5th laboratory scale combined multi-stage series connection piston flow reactor is set, import in it with the porch of the middle first order reactor of described the 5th multistage reactor and to have selected effluent and the hydrogen that is pressed in that divides, so that hydrocarbon molecules hydrocracking and isomerization in the effluent from the afterbody reactor of the 4th multistage reactor; Beds in each stage reactor of described the 5th combined multi-stage reactor comprise can catalysis by make hydrocarbon molecules hydrocracking and the isomerized catalyst granules in the effluent in the first order reactor that is input to described the 5th multistage reactor by hydrogen; Describedly make that the hydrocracking of hydrogen compound molecule and isomerized operation are to carry out in the effluent under the operating condition of selected one group of temperature, pressure, reactant flow velocity and product flow velocity, the catalyst in the beds in described the 4th laboratory scale reactor has optional features;

Z1) effluent of each stage reactor of described the 5th multistage reactor is sampled;

Z2) product that generates by catalytic reaction in the effluent of each stage reactor of described the 5th multistage reactor of measurement and the concentration of accessory substance;

Z3) at repeating step z under the selected different described operating condition and/or under selected different specificity of catalyst) to z2); With

Z4) utilize the result who in hydrocracking and isomerized operation, measures gained to be chosen in the characteristic and productive rate and the selectivity of operational factor of the beds in follow-up hydrogenation cracking and the isomerized operation to improve described the 5th laboratory scale piston flow reactor.