• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    The invention relates to a process for separating at least one catalyst or adsorbent from a homogeneous mixture of catalysts or adsorbents, the catalysts or adsorbents having been used in a gas treatment process or hydrocarbon feedstock, process in which the catalyst or adsorbent grains are separated according to a sorting threshold corresponding to a content of the constitutive element sought and defined by the operator. The catalyst or adsorbent grains pass in front of the detection system LIBS, which detects the presence of said desired element for the wave length (s) characterizing said element, the analyzer associated with the LIBS processes the signal sent by the detector by comparing it with a significant set value of the sorting threshold, and sends a signal to a catalyst grain removal means so as to separate said grains from other catalysts and / or adsorbents of said mixture. At least one of the catalyst batches that are lightly charged with said element is recycled to the gas treatment process or the hydrocarbon feedstock after a possible regeneration.
    公开号:FR3036981A1
    申请号:FR1555165
    申请日:2015-06-05
    公开日:2016-12-09
    发明作者:Thierry Gauthier；Charles-Philippe Lienemann；Wilfried Weiss；Pierre Dufresne；Pauline Galliou
    申请人:Europeene de Retraitement de Catalysateurs EURECAT；IFP Energies Nouvelles IFPEN；
    IPC主号:
    专利说明:

    [0001] The invention relates to a process for separating at least one catalyst from a homogeneous mixture of catalysts, this separation being based on a detection of difference in composition using LIBS technology, and at least one of these catalysts is then regenerated. to be reused for a new catalytic cycle.
    [0002] PRIOR ART There is a wide variety of types of catalysts and adsorbents. A significant tonnage relates to applications in the field of petroleum refining, petrochemicals, chemicals, and natural gas processing. The catalysts contain constituent elements (metals) which give the catalyst the catalytic properties required to treat certain gaseous flows or petroleum cuts, such as Ni, Co, Mo, W especially for hydrotreating and hydroconversion catalysts, such as Pd , Pt, Ni, Cu, Cr, especially in processes of hydrogenation, dehydrogenation, isomerization, reforming, hydroconversion. One of the refining processes using catalysts is hydrotreating, which consists of treating petroleum feeds to either convert them to lighter products or to refine them, that is, to purify them. The hydrotreatment / hydrocracking catalysts consist of an active phase of the Ni, Co, Mo or W metal sulfide type supported on alumina or on silica-alumina. These catalysts are used in reactors under hydrogen pressure, which contain from a few tens to a few hundred tons of catalysts. A reactor always contains different types of catalyst. Although they are generally of the same family, namely containing the metals Ni, Co, Mo or VV, they can be of different shape or different composition. The cycle time of a catalytic hydrotreating reactor is from 1 to a few years. At the end of a cycle, the performance of the catalysts has dropped so much that the unit must be shut down and the catalysts discharged from the reactors. Then they can be treated as waste or then undergo an oxidative regeneration which allows them to find performances close to new products.
    [0003] Today, only about 20% of these hydrotreatment / hydrocracking catalysts are regenerated after evaluation and then reused. The remaining 80% becomes treated waste for recovery of recoverable metals. This regeneration rate is low, and this leads to additional costs for the user sector and losses of 5 strategic metals, the recycling of metals always taking place with yields well below 100%. The reasons for the non-regenerability of the hydrotreatment catalysts are four in number. The first is a sintering of either the carrier or the active phase, and the catalyst is considered unrecoverable. The second is contamination: the catalysts are polluted by elements carried by the oil load. This is the case with vanadium contained in the heavy fractions of the crude oil. The third reason is that they have lost some of their properties, particularly strength properties. So they become too fragile or improperly shaped to be reused. These three reasons for non-regenerability are conventional and do not only concern hydrotreatments but apply to many other types of catalyst. A fourth reason relates more specifically to this invention. It also extends beyond the field of refinery hydrotreatments. The non-regenerability can come from the fact that several types of these catalysts are loaded in the same reactor, this to optimize the overall performance of the reactor, the catalysts having various activities or selectivities for different reactions. During unloading operations of the reactors at the end of the cycle, the catalysts are inevitably mixed with each other. Indeed, even when the catalysts are loaded separately in layers (beds or stacks) distinct, the emptying has the effect of mixing these different layers, because experience shows that the emptying process follows an hourglass-type law, and not a piston flow law 3036981, resulting in a mixture of all layers of possibly different products. In this case, the caalysers are no longer reusable, users requiring to recharge catalysts of a specific type and not mixtures. Such mixtures are considered as waste, directed to recycling channels for metal recovery. For example, hydrotreating reactors are often loaded with several types of catalysts; thus, different commercial names, different compositions which allow different catalytic actions, for example catalysts CoMo and NiMo (mixture of cobalt / nickel and molybdenum and alumina), or catalysts NiMo / support alumina and NiVV catalysts (Nickel If they have different particle sizes, they are separable by mechanical sorting: if they have the same particle size, and if they have been loaded into the same bed of the same reactor, they will be discharged in the same way. They can not be reused as a mixture after regeneration, and therefore become waste because no known technique allows them to be separated.Some dehydrogenation catalysts, containing chromium at a level of 10 to 25% of Cr 2 O 3, can be used not in the pure state but in admixture with an inert, non-catalytically active product, typically an alumina, for reasons of balance When the catalyst is worn, it is discharged with its diluent. It is therefore expedient to separate the metal-containing catalyst from the aluminum diluent to optimally recycle the catalyst. This is the problem raised by this fourth reason that the invention proposes to solve. DESCRIPTION OF THE INVENTION The invention more specifically relates to a process for separating at least one catalyst or adsorbent from a homogeneous mixture of catalysts and / or adsorbents, said catalysts or adsorbents having been used in a treatment process. of gas or hydrocarbon feedstock, in which process the catalyst or adsorbent grains are separated according to a sorting threshold corresponding to a content of said element and defined by the operator, in which process the catalyst particles of said mixture pass through. in front of a detection system LIBS which detects the wavelength characterizing said constituent element, the analyzer associated with LIBS processes the signal sent by the detection system by comparing it with a significant setpoint value of the sorting threshold, 5 - 1 analyzer sends a signal to control the removal of grains its content of said element and is obtained at least 2 batches: at least one batch ca catalysts heavily loaded in said element with respect to the sorting threshold and at least one batch of catalysts with little charge in said element with respect to the sorting threshold, and at least one batch of catalysts with little charge in said element is recycled. in said gas treatment process or hydrocarbon feedstock after a possible regeneration. The invention can also be applied to adsorbents, or mixtures of catalysts and adsorbents. The term "constitutive element" means a component of the composition of the catalyst or of the adsorbent in the fresh (or new) state. that is, before use in gas treatment processes or hydrocarbon feedstock. The invention is preferably implemented when the catalyst to be separated contains as constitutive element a non-metallic element, preferably chosen from the group formed by phosphorus, boron, lithium, sodium, potassium, calcium, the chlorine, silicon or constituent element is metallic and is preferably aluminum, titanium or chromium, copper, zinc. More specifically, the invention relates to a method and a device for sorting phosphorus-containing catalysts or adsorbents from other phosphorus-free catalysts or adsorbents, or having a significantly lower phosphorus content.
    [0004] More specifically, the invention relates to a process for sorting a boron-containing catalyst or adsorbent from other boron-free catalysts or adsorbents, or having a significantly lower boron content. The invention more specifically relates to a method for sorting a catalyst or adsorbent containing silica-alumina, amorphous or crystallized (zeolite), other catalysts or adsorbents without silica-alumina. In this case, the compositional detection can be performed on the Si element contained in the fraction containing the silica-alumina. More specifically, the invention relates to a process for sorting a chromium-containing catalyst from a mixture with other non-catalytic and non-catalytically chromium-free solids. These other solids may be a diluent consisting essentially of alumina, which is found in the guard bed which is at the top of the reactor, and which comprises one or more catalytic beds downstream of the guard bed. The invention more specifically relates to a method and a device for sorting a catalyst containing a hydrotreatment catalyst said to be mass or unsupported, containing mainly metals in the oxide or sulphide state (greater than 50% by weight), other catalysts supported on metal content (less than 30%). In the case where the carrier of the supported catalyst is alumina, the compositional sorting can be carried out on the element Al. The catalysts are used in gas treatment processes of different compositions or hydrocarbon feedstock treatments. Among the gas treatments, mention may be made of the Claus process, and tail gas treatments. For the hydrocarbon feedstocks, mention may be made of the catalysts used in the processes of hydrotreatment, hydrocracking, hydroconversion of distillates, as well as applications of hydrogenation, dehydrogenation, isomerization and reforming.
    [0005] The support generally based (or is advantageously constituted) of alumina, silica-alumina, titanium oxide; in the hydrocracking, hydroconversion catalysts, zeolite (crystalline silica-alumina) may be present. According to the invention, the passage time of a grain in front of the LIBS detection system is less than 50 ms (millisecond), and preferably less than 10 ms.
    [0006] The method according to the invention makes it possible to detect and sort a number of grains greater than 20 grains per second, preferably greater than 50 grains per second, and even greater than 100 or 200 grains / set up to 1000 grains. / s or more. Preferably, the grains flow so that their spacing is between zero and their largest characteristic dimension. The measurement frequency is 3036981 6 between 1 / t and 1 / 2t, t being the passage time of the grain in front of the LIBS detection system. Advantageously, the spacing between the grains is at most equal to their largest characteristic dimension. This maximizes the amount of material processed for a given grain flow rate. Advantageously, the detection system is positioned so that the depth of the analysis field above the surface of the transport means is between 1/3 and 3 times the smallest characteristic dimension of the grain. The object of the invention is to propose, for catalysts or adsorbents, which are objects of homogeneous and well-defined shape (extruded cylindrical, trilobe or multilobe, balls), a sorting process based on the means of very fast detection online LIBS. Catalysts or adsorbents: Catalysts are well-defined objects in shape, size and composition. Their mixture is separable according to the invention when this mixture is homogeneous, and of course when there is a difference in the constitutive element (s) (presence or not, content) and this difference is detectable by LIBS. The length of the extrudates has a certain distribution around an average value, this being due to a certain variability of length during the production of the catalysts or adsorbents, but also to phenomena of attrition and breakage of the extrudates which have 20 effect a certain reduction in length. In the rest of the text, the largest characteristic dimension will be called the average length of the extrusions. By smaller characteristic dimension of a particle is meant the diameter for a cylindrical ball or extrusion, or the circumscribed diameter tangential to the apices of the lobes for a trilobe or a multilobe. In general, the term diameter will be used throughout the text as the smallest characteristic dimension regardless of the type of particle. The diameter of the particles (or grains) is generally well defined and its dispersion is generally small compared to its mean value.
    [0007] The homogeneous mixture According to the invention, the catalysts to be sorted are in the form of a homogeneous mixture. The term "homogeneous mixture" means a mixture in which the catalysts have a homogeneous size and / or a homogeneous shape. "Homogeneous size" means that the 5 diameters are very close. In general, the catalyst is in the form of cylindrical, trilobe or quadrilobe or multilobe beads or extrudates of diameter often between 0.5 and 3 mm (often close to 0.9-1.5 mm) and of length equal to 2 to 5 times the diameter. extruded. It can be shaped in the form of beads of 0.5 to 10 mm, preferably between 0.5 and 5 mm in diameter, or pellets. The catalysts can also be used in the form of dispersed powders, the diameter of which is in general less than 200 microns, but this shaping does not concern the object of the invention. Figure 3 shows grain shapes. It should be noted that these forms sometimes have defects inherent to the production method. For example, extrusions are sometimes slightly curved along the length. These defects are acceptable in carrying out the process according to the invention. This homogeneous mixture could be obtained at the end of a preliminary separation step (pre-sorting) based on the physical properties. This pre-sorting can be carried out on catalysts having a different diameter. This pre-sorting can also be carried out on a mixture containing grains of similar diameter, but for which it will be desired to eliminate too short particles, which are not reusable, and which should be removed before the compositional sorting. This pre-sorting can be carried out, for example, by sieving or other technique known to those skilled in the art to separate solids by their size, or any other sorting method (sorting by density ...). This pre-sorting is interesting for example to separate the elements loaded at the top of the reactor, said elements of the guard layer, or the guard bed. These elements are often mixed during unloading with the catalysts located in the lower layers. These elements may be beads, rings, extrudates, pellets, containing or not catalytic elements. They must be separated before the valorizable catalysts or adsorbents are subjected to the composition sorting system with detection LI: This pre-sorting is also advantageous in the case of catalysts of different shape (for example cylindrical or multilobed) having diameters different, for example a mixture of 1.5mm and 3mm. Conventional techniques of mechanical separation, sieving for example, can be implemented to recover each product. It may also happen that in the same reactor are charged two catalysts or adsorbents of the same shape and size but of different composition. In this case, the invention makes it possible to solve the problem posed by the selective recovery of one or more of the components of the mixture. The constituents of the catalyst The support of the catalysts or adsorbents is generally based (or preferably constituted) alumina or silica-alumina or titanium oxide, with the possible presence of zeolite especially for hydrocracking catalysts, hydroconversion of distillates or hydrotreatment. The catalysts contain constituent elements (metals) which give the catalyst the catalytic properties required to treat certain gaseous flows or petroleum cuts, such as Ni, Co, Mo, W especially for hydrotreating and hydroconversion catalysts, such as Pd , Pt, Ni, Cu, Cr, especially in processes of hydrogenation, dehydrogenation, isomerization, reforming, hydroconversion. The active phase of the hydrotreatment and hydrocracking catalysts contains cobalt, nickel, molybdenum or tungsten sulfides, which are supported, generally on alumina. The new catalyst is initially prepared with oxides of these metals, which are then sulfided. Depending on the reaction objectives in general, the combinations CoMo, NiMo, NiCoMo or NiVV are found. The initial composition of nickel or cobalt oxides generally being between 2 and 10% by weight on the catalyst and the composition of molybdenum or tungsten oxides being around 15 to 30% by weight. There is also the case of unsupported, so-called bulk catalysts, which then essentially contain mixtures of metal salts in their composition, for example essentially in the activated state of the sulphides of Ni, Mo, W.
    [0008] The catalyst contains or does not contain phosphorus or boron, which are dopant type elements used to improve the performance of the products. The hydrotreating reactor may contain different catalysts of the same shape and composition different in P and B and which can not be reused as a mixture after unloading the reactor.
    [0009] The invention then makes it possible to sort phosphorus-containing catalysts from other phosphorus-free catalysts, or having a significantly lower phosphorus content, or a boron-containing catalyst from other boron-free catalysts, or having a significantly lower content of phosphorus-containing catalysts. lower in boron. The catalyst contains or does not contain silicon, this is the case for catalysts having a support containing silica-alumina. This may be of amorphous or crystalline type, in which case it is generally a zeolite. This amorphous or crystalline alumina silica is added for example when an acid function is desired to promote the cracking of hydrocarbon molecules. The hydroconversion catalysts contain the element Si at contents of between 1 and 45%, preferably between 2 and 40%, and more preferably between 3 and 30%. As a reminder, hydrotreatment catalysts contain Si contents often less than 2 or even 1%. Some hydrocracking catalysts contain, for example, a NiMo or NiVV phase associated with a mixture of zeolite (or amorphous silica-alumina) and alumina. They are generally charged to a reactor located downstream from another reactor containing one or more NiMo / alumina catalysts. But sometimes they are loaded into the same reactor in the lower layers of this reactor. They are often loaded into separate beds of these reactors, but in some cases they may be in the same bed. At unloading, for different types of reason, there may be a mixture between these two types of catalyst.
    [0010] Other specific hydrocracking applications fall into the category of dewaxing or hydrodewaxing, or catalytic dewaxing. The application aims at selectively removing linear paraffins which deteriorate the cold-holding properties of the gas oil, or the characteristics of the lubricants. An example is shown in US Pat. No. 4,347,121 to Chevron, which describes the linking of a dewaxing catalyst with a hydrofinishing hydrotreating catalyst. The dewaxing catalyst consists of zeolite type ZSM5 and alumina, while the finishing catalyst contains Pd and silica alumina. The invention makes it possible to separate mixtures of these types of catalysts by virtue of their different composition. Another case of mixing is illustrated in US Pat. No. 8,063,261, which mentions the use of alumina eta mixed with a chromium-containing catalyst in the application of dehydrogenation of a hydrocarbon feedstock of C3 or C4 to make propylene or butenes. These dehydrogenation catalysts may contain 10 to 25% chromium Cr 2 O 3. They can be used in a widely used process commercially known as the Catofin process. For reasons of thermal balance of this process, the catalyst is not used pure, but in admixture with an inert, non-catalytically active product, typically an alumina, which serves as a diluent, for example up to 50% by volume. When the catalyst is worn, it is discharged with its diluent. It is therefore appropriate to separate the metal-containing catalyst from the aluminum diluent to optimally recycle the catalyst. LIBS technicaue by LIBS technique LIBS is a basic analysis technique, which is increasingly used for the direct compositional analysis of solids and liquids. The growing interest in this technique stems from its many advantages including in this case a possible in-situ analysis without special sample preparation, rapid analysis, simplicity of use, precise focusing. The principle is based on the focusing of a laser pulse on the surface of the sample. This focusing of laser pulses of a few nanoseconds, or even femto seconds, and an energy of the order of a few tens of milli joules towards the point to be analyzed on the material causes the formation of a micro-plasma. This micro-plasma feeds on the composition of the surface of the sample, which generates the vaporization and ionization of the material, and then cools over time. The size of the analysis point is usually of the order of a few microns or even ten microns. The atoms and ions of the material present in the micro-plasma, emit by de-energizing photons whose wavelength is characteristic of the chemical element. A spectrometer in the UV / visible domain collects, possibly using an optical fiber, and translates the light emitted by the plasma. The emission lines, generated by the sample analyzed, make it possible to identify the elements present in the sample (qualitative analysis) and thus to know the chemical species that made up the sample. Their intensity can also be measured and compared to that measured for a range of samples of known concentration, in order to measure the elemental composition of the sample (quantitative analysis). In the case of the present invention, a quantitative analysis makes it possible to measure the constituent element content on the catalyst or adsorbent to be separated, for example the phosphorus content on a hydrotreatment catalyst. The speed of response of LIBS is a decisive advantage for the productivity of sorting with small objects such as catalysts. The catalyst or adsorbent grains are subjected to laser radiation. In return, in an analyzer, the associated emission is analyzed by spectroscopy at a chosen wavelength to allow the detection of the constituent element on the catalyst and preferably to measure the intensity of the peak (s) relative to this element. To do this, the analyzer associated with the LIBS processes the signal sent by the detection system by comparing it with a significant setpoint value of the presence of the element, and preferably also significant of the sorting threshold.
    [0011] The sorting threshold may correspond to 0% wt and therefore the presence or absence of the desired constitutive element is detected and sorting is performed on this presence or not, 0% corresponds to the detection limit of the LIBS for l considered element. The sorting threshold may correspond to a content different from 0%, chosen by the operator depending on the element sought and the contracte / objectives of the operator. The threshold of the element is chosen to allow separation of the element from the mixture. The wavelengths associated with the contaminant are known to those skilled in the art, as well as the possible interference with other elements. The Na is emissive and measurements of content on the catalyst grains are possible up to contents as low as 0.1%, which makes it possible to sort the catalysts as a function of a threshold value of tri) chosen by the operator in the range between 0.5 and 2% wt in Na, For example, for phosphorus, many atomic emission lines between = 178 and 254 nm are used for their high intensity and their absence of interference with the constituent elements of the catalyst. Alternatively, the lines at a wavelength of 214.920 or 203.240 nm are used alone or in combination with any other spectral line constituting the sample. The sorting may be carried out on catalysts containing In the case of boron, which may be a constituent element of a hydrotreatment catalyst, the wavelengths for the detection may be 249,772 and 249,677 nm. The sorting may be carried out on catalysts containing a threshold value of between 0.5 and 2% by weight of B. In the case of chromium, the sorting threshold value chosen by the operator in the interval may be between 3 and 6% wt Cr.
    [0012] In the case of silicon, to meet a number of mixture separation requirements, the detection threshold can be set from 1 to 3% by weight. In the case of aluminum, it may be that both catalysts contain aluminum, but in a significantly different concentration, for example 40% Al for a typical hydrotreatment catalyst, and 10% for a zeolite catalyst. or alumina serves only as a shaping link. In this case, the signal strength serves as a discriminating criterion and the threshold in this example would be set to 20 or 30 wt%. The Al line is at 308.852 nm. It should be emphasized that the thresholds indicated above are indicative and that it is naturally possible to have higher values depending on the sorting constraints desired by the operator. In order to improve the detection sensitivity, it is possible to carry out an analysis at several wavelengths, for example using several spectrometers coupled on the same light beam and operating in parallel.
    [0013] The detection system is preferably adjusted so that the depth of field of the analysis above the surface of the transport means is between 1/3 and 3 times the smallest dimension characteristic of the catalyst grain. (The diameter of the extrudate in the case of a substantially cylindrical particle, the diameter of the grain in the case of a spherical particle) to allow ultrafast detection of the composition of the grains. In practice, the analyzer makes it possible to restore the composition in the desired element with a response time t of less than 50 ms, preferably less than 10 ms. The passage time of a grain in front of the detection system is less than 50 ms, and preferably less than 10 ms and can be up to less than 1 ms. The number of grains detected is at least 100 grains / s for a detection time of less than 10 ms. It can reach 1000 grains / s for a ventilation time of less than 10ms. In a preferred form of the invention, the catalyst particles are spaced apart, preferably regularly, by a distance preferably corresponding to the greatest characteristic dimension of the catalyst grains, ie the average length of the catalyst grains. The measurement / detection is repeated at intervals of time. When the grains are spaced apart from their average length, the measurement frequency is equal to 1 / 2t, t being the passage time of the grain in front of the detection system. When the grains flow contiguously (the grains are contiguous, their spacing is zero), the frequency is equal to 1 / t. More generally, the grains, preferably extruded cylindrical or multilobe, flow so that their spacing is between zero and their length, the measurement frequency is between 1 / t and 1 / 2t t being the passage time of the grain in front of the LIBS detection system. The spacing between the grains is controlled by the means set according to the detection time of the LIBS detection system. The spacing may advantageously be equal to or less than the average grain length.
    [0014] For example, it is the means for controlling the feed (flow rate) of the catalyst grains on the transport means (tread, vibrating belt, etc.) and the speed of said means. In general, the process conditions are adjusted so that it is treated with a grain count greater than 20 grains per second, up to 1000 grains per second, and with a LIBS detector. response of the LIBS detection system is less than 50 ms, preferably less than 10 ms. Optionally, the presence of the grains can be detected by means of another optical device, for example a camera, so that the triggering of the laser of the LIBS system is synchronized with the passage of the grain under the beam of the laser. In a preferred embodiment of the invention, each catalyst grain is exposed to the detection system. In a preferred embodiment of the invention, it is then possible to treat at least 20 grains per second with the same measuring apparatus, for example 20-100 grains / s, preferably more than 100 grains per second, and up to 1000 grains per second or more. It is also possible to have several detection systems in parallel to operate at high rates. Thus the use of 5 parallel detection systems operating at 200 grains / s will achieve a flow rate of 1000 grains / s.
    [0015] Determination of the Elemental Element The LIBS system measures the intensity of the peak (peaks) relative to the contaminant. The operator chooses a value of the sorting threshold included in the values indicated above, or higher, according to his sorting needs. The spectrometric analysis at the wave length (s) considered allows (e) to go back to the mass concentration of the constituent element by means of a preliminary calibration. According to the calibration performed by the operator, the setpoint (corresponding to the presence of contaminant or the sorting threshold) is entered in the LIBS system. It may be either a content 3036981 or any other value significantly related to the content (it may be the intensity of the peak ...), all these techniques are well known to those skilled in the art. After comparison between the setpoint and the measured value, the system acts to evacuate the grain to the corresponding storage. It must be emphasized that the presence of a specific element can be correlated with the content of another element. This is an advantage if one of the two elements is more easily detectable in LIBS, because of one or more lines more emissive, or because of interference of another element disturbing the signal of a contaminant but not the other. This may also be a deliberate choice relating to the use of a spectrophotometer whose spectral band includes the lines of one element and not the other. The separation of the nests When the detection system LIBS detects the constitutive element in one or more grains and preferably also determines the state of the grain with respect to the sorting threshold, it sends a signal to a means of evacuation of this element. grain to be separated so as to separate said grain from said mixture. The detection system is connected to a control system of the grain evacuation means containing the desired characteristic element. These means are located at the level of the transport means (treadmill ...), and most often they are located at the downstream end (outlet) of the means of transport.
    [0016] These means are operated with a time shift depending on their distance from the detection system. An example of an evacuation means for directing grains in different directions is the use of compressed air. The jet of compressed air or the absence of a jet of compressed air makes it possible to direct the grain towards the various sorting classes, for example the grains containing more than X% of a desired element discharged upwards whereas the grains containing less than X% of this element are evacuated downwards. For example, if the catalyst or adsorbent grain contains the desired element at a content greater than the sorting threshold set by the operator then the means are actuated and allow a deflection of the grain flow to a receptacle A. If, on the contrary, the catalyst or the adsorbent contains the contaminant with a content less than or equal to the threshold of sorting fixed by the operator then the means are not actuated and the catalyst flows normally to another receptacle B In the case where it is desired to sort the catalysts or adsorbents as a function of several contents in different elements, advantageously several LIBS detection systems are available, each having a wavelength adapted to the characteristic element to be separated. The evacuation means are adapted accordingly. We will not detail here the multiple possibilities of sorting, sorting can be multiple in the presence of several detectors LIBS. Those skilled in the art will adapt the process according to the invention according to their needs.
    [0017] The method according to the invention can advantageously be implemented with the device described hereinafter with the aid of the figures. Figure 1 shows an illustrative embodiment of a preferred embodiment, Figure 2 shows a castellated carpet. Figure 3 shows grain shapes. It is a device for separating at least one catalyst or adsorbent from a homogeneous mixture of catalysts and / or adsorbents, said catalysts or adsorbents containing at least one constituent element and having been used in a process for the treatment of gas or hydrocarbon feedstock, the separation and sorting device for separating the catalysts or adsorbents according to a sorting threshold corresponding to a content of the constitutive element desired and defined by the operator, the device comprising: transporting the catalyst mixture provided with a conveying means, grain flow rate controlling means on said means and means for controlling its speed, said means being adjusted so that the passage time of a grain in front of the detection means LIBS is less than 50ms, and preferably less than 10ms and the number of sorted grains is at least 20 grains / s, preferably at least 100 grain / s and even more preferably at least 200 grain / s, - a detection system LIBS comprising at least one laser in front of which the grains pass, the detection time being less than 50 ms, and preferably, less than 10 ms, and the wavelength being that of the desired constitutive element, said system detecting the charged grain in said desired element and measuring the intensity of the peak associated with said wavelength, 3036981 17- at least one analyzer (8) and at least one control means (10), said analyzer processing the signal sent by the detector by comparing it with a significant reference value of the sorting threshold, - at least one means for discharging the grains at separating, the said means (s) being actuated (s) from said control means according to the content of said desired constituent element. Conventional conveying means (vibrating tube, vibratory elevator, etc.) and storage of grains to be sorted and sorted grains can be used at different points in the sorting process.
    [0018] Advantageously, the means of transport is a tread (or conveyor belt). It can also be a die provided with a worm dug in its axis and provided with at least one opening adapted to the detection and at least one opening adapted to the separation of the catalyst particles. This means of transport can also be a carpet or a vibrating tube.
    [0019] Preferably, the transport means is a treadmill and preferably crenellated, the depth of the crenellations being between 0.5 and 3, and preferably 0.7 and 1.3 times the smallest characteristic dimension of the grains, corresponding to the diameter in the case of a sphere or an extrusion. Preferably, the adjustment of said means of the conveyor chain is carried out so that the grains flow with a spacing between zero and their largest characteristic dimension, the measurement frequency is between 1 / t and 1 / 2t, t being the passage time of the grain in front of the LIBS detection system. The grains are preferably extruded cylindrical, trilobes or multilobe. When the grains are spaced apart from their mean length, the measurement frequency is 1 / 2t, where t is the time the grain passes in front of the detection system. When the grains flow contiguously (the grains are contiguous, their spacing is equal to zero), the frequency is equal to 1 / t. The device of the invention is particularly well suited to implement the method of the invention. Also, the features described previously for the method apply to the device.
    [0020] Advantageously, the detection system is placed so that the depth of the analysis field above the surface of the transport means is between 1/3 and 3 times the smallest characteristic dimension of the grain. Advantageously, the passage time of a grain in front of the detection system LIBS is less than 50 ms, and preferably less than 10 ms, the analyzes being repeated at intervals of time at most equal to the passage time of the grain of more small characteristic dimension. DETAILED DESCRIPTION OF THE SEPARATION METHOD AND DEVICE: The catalyst particles initially stored in drums, containers, silos or bags and then are generally transferred to a buffer capacity, for example a hopper, this capacity feeding a chain transport which advantageously comprises an unwinding strip such as a treadmill or a vibrating tube or corridor, and which comprises means for controlling the grain flow rate on the tread.
    [0021] The transported grains pass in front of the LIBS analysis system making it possible to determine whether the grains have a content that is less than or equal to or greater than (or less than, greater than or equal to) the desired element with respect to one or more sorting thresholds defined by the operator. There may be one or more thresholds for each item depending on the needs of the operator.
    [0022] FIG. 1 is illustrative of a preferred but non-limiting embodiment. The unsorted catalyst seed mixture (1) is fed to a means (2) for controlling the grain flow rate on the tread (5). The feed means of the mixture (3) can be manual (bag unloading for example) or automatic (by controlled discharge of a silo for example).
    [0023] The invention is described with a tread as conveyance but the description is quite transferable with another means of transport, such as for example a vibrating corridor. The means for controlling the flow rate are means well known to those skilled in the art, such as inclined vibrating plates, allowing the uniform spreading of the catalyst grain and adjusting the catalyst flow rate on the catalyst. the plate towards the tread. Those skilled in the art can thus adjust the distance between two grains on the transport chain and adjust the detection frequencies accordingly or, conversely, it can adjust the distance as a function of the detection frequencies.
    [0024] By way of example, in FIG. 1, we have shown in (2) a vibrating plate in two orthogonal directions. With this type of equipment, it is possible to adjust the vibration frequencies to modulate the flow of solid (4) to the tread (5), adjust the distribution between the grains on the passage section and thus control the spacing between the grains as a function of the speed of movement of the web.
    [0025] Preferably, the device will be optimally adjusted so that the distance between the grains is at most equal to the average grain length. At the outlet of the flow control means (2), the catalyst grains fall on the tread, which may be a simple flat treadmill, or a castellated belt, as shown in FIG. 2.
    [0026] The crenellated carpet of FIG. 2 is of obvious interest in particular when extrusions are sorted in that it advantageously allows the grains to be oriented in the direction of flow. The grain flow is thus more even and spaced, which promotes detection, separation and improves the productivity of the plant. In general, irrespective of the shape of the grain, the crenellated carpet prevents the grain from moving under the effect of the vibrations of the carpet and / or pulses of the laser. In the case of a crenellated carpet (20), a crenellated form (21) in the form of an equilateral triangle as shown in Figure 2 is advantageous; the depth of the crenellations on the carpet is then ideally between 0.7 times and 1.3 times the largest characteristic dimension of the grains, the diameter of the catalyst grains in the case of the balls, the average length in the case of extruded cylindrical or trilobes. or multilobe. The grains (22) are positioned on the carpet (20). The forward speed of the belt is adjusted to optimize the production capacity on the one hand, and the ability of the system to detect. the desired contaminant in the catalyst grains.
    [0027] It will be preferentially sought for the passage time of a grain to be less than 50 ms, and preferably less than 10 ms. More generally, the passage time is as low as possible in accordance with the response time of the detection system. Under these conditions, for example, for a cylindrical extrusion of length equal to 5 mm, the speed is preferably between 0.1 and 5 m / s. The detection system comprises at least one laser (6), at least one spectrometer (or analyzer) (8) and at least one means (10) for controlling the opening or not of at least one evacuation means. A laser (6) emits radiation focused on the surface of the sample (7). Following the pulse of the order of the femto-nanosecond between the laser and the sample, a plasma fed by the composition of the sample is generated and returns in milliseconds wavelengths specific to the composition of the sample (9). The emissions from the sample (9) are analyzed by a spectrometer (8) at the specific wavelengths of the contaminant to be detected. Optionally, at least one optical fiber is used between the plasma and the spectrophotometer. It is possible to work at several wavelengths simultaneously by positioning on the light beam several spectrometers in parallel which work simultaneously at different wavelengths. For example, to measure the element content in the hydrocracking catalysts or dyes. hydrotreatment, we will use the (or) wavelength of significant intensity. According to the needs, it is possible to analyze all the grains passing in front of the detection system (6-7-8-9) on the tread (5), globally or individually, by using several laser systems ( 6) in parallel so as to cover the width of the strip and also adapting or uncoupling the laser and the spectrometer (8) analyzing the emissions (9). It is also possible to choose to operate statistically, by analyzing only a fraction of the flow, or to consider a displacement over the width of the lasers (6) and the spectrometer (s) (8).
    [0028] The analyzer (the spectrometer) (8) is connected to control means (10) for converting the results of the analysis into action to act on said evacuation means (here the valve 12). These means consist for example of a computer for triggering the opening of a valve (12). Thus, for example when the analyzer (8) detects that the grain has a content greater than the set value (for example at the sorting threshold), it sends a signal to the control means (10) which actuates the opening of the valve (12). It is located on an inert fluid pipe (air, for example) under a pressure, if possible, greater than 5 bars (preferably air) to promote the creation of a jet of gas (air) sufficient to evacuate the grain. The valve (12) opens for a specified period of time and then closes automatically. The opening of the valve generates a jet at the lower end of the pipe (11). It acts with the pipeline as a gas ejection nozzle (air).
    [0029] Advantageously, the pipe (11) is positioned at the end of the conveyor belt at a distance of not more than 10 cm from the end of the belt (depending on the speed of advance of the belt, the more the unwinding speed of the belt is the pipe (11) is brought closer to the end of the belt), at a height above the belt (5) preferably between 2 and 10 times the largest characteristic dimension of the catalyst grain (its length in the case of an extruded). It is possible to position one or more pipes (11) in parallel depending on the width of the conveyor belt and the shape of the end of the pipe. In the case of a spherical pipe end, the diameter of the tip of the pipe is preferably less than or equal to the average grain length.
    [0030] If the carpet allows the simultaneous passage in the width of N particles simultaneously, up to N tubes (11) can be positioned in parallel, each having their valve, the valves being controlled simultaneously or separately by the means (s) control (10) depending on the number of analyzers used in parallel.
    [0031] 3036981 22 It is also possible to work with a single pipe (11) but whose end of rectangular section could create a jet of gas brush, the thickness of the jet being., While preferentially less than or equal to the largest characteristic dimension of gu: dn. In order to take into account the distance between the detection means and the evacuation means, the control system triggers the closing opening cycles with a delay which is a function of the distance to be traveled between these two points. For example, if the carpet length between the focal position of the analyzer on the belt (9) and the means (s) of evacuation (valve, air injection nozzle (12)) is 3 m and that the speed of travel 10 on the belt is 3m / s, a delay of one second is to be taken into account, to be corrected possibly depending on the response times of the analyzer (8), the means of control (10) or valve (12) For the purposes of the invention and to be selective, the opening-closing cycle of the valve must be fast and consistent with the passage time of grains in front of the detector.
    [0032] Preferably, the closing opening cycle time will not exceed 1 and 5 times the passage time of the grain in front of the detection means, preferably less than 3 times this average passage time. Thus, the valve and actuator technologies will be chosen in order to have a closing opening cycle of between 5 and 250 ms as a function of the running speed of the transport means (5). The jet of gas (for example air) created during this period has a speed at least equal to 5 times the final rate of drop of the catalyst grain, preferably 10 times the terminal drop speed (in the case of an extruded hydrotreatment, the terminal drop speed is generally close to 5 m / s and between 2 and 7 m / s. When the actuator triggers the opening of the valve, the jet of gas deflects the trajectory of the grain towards a receptacle ( 14) that collects all the grains in the contaminant content is greater than the operator defined sorting threshold.If the actuator is not triggered, then the path of the grain coming out of the conveyor belt describes a normal parabola according to The speed of unwinding of the carpet and the final rate of falling of the particles, the grain then falls into a receptacle (13) which collects all grains to be eliminated not containing the undesired element.
    [0033] Thus, the grains collected in (13) will constitute a new batch having, for example, an element content below the sorting threshold defined by the operator. Compared to the prior art, the invention allows rapid sorting according to the desired element content of at least 20 to 100 objects (catalyst particles) / second, generally at least 50 or even 100 objects / second, or even beyond 100 objects / s and its use allows up to 1000 objects / second or more. The LIBS technique alone thus allows significant productivity. Another advantage of the invention is that it can be used in the air or any other atmosphere (not interacting with the detection or the grains).
    [0034] EXAMPLES Example 1: Sorting a batch of NiMoPB and NiMoP catalyst mixes Two NiMoPB and NiMoP type catalysts were mixed. 40 grains of mixture were analyzed by LIBS to determine the presence or the absence of boron on these grains of catalysts. A laboratory LIBS device (MobiLIBS III, IVEA) was used for this test and is composed of a laser (Brio, Quantel, Nd-YAG at 532 nm) and a spectrometer (Mechelle Andor, 200-900 nm). . A single shot of the laser was F8qUis and each grain of catalyst was analyzed under the following conditions: 12 mJ / 140 pm spot / 3-5 ns pulse time. The doublet of B lines at a wavelength of 249,772 and 249,677 nm was used. A signal close to 2000 rounds on the line at 249.772 nm and a little weaker on the second line is observed in 43% of the grains analyzed. On the small amount of material harvested during this sorting, 100 mg of each of the two categories formed by sorting was cold-mineralized for an ICP / OES (ICP Spectro Arcos) assay. The average boron content on the grains generating a signal of 2000 rounds on the line at 249.772 nm is 1500 mg / kg whereas the boron is not detected in the mineralized material formed by the grains having given no signal of boron. The sorting carried out on the basis of the detection of B on the doublet 249.772 and 249.677 nm is therefore effective for discriminating the boron-containing or non-boron-containing catalyst grains.
    [0035] EXAMPLE 2 Mixture of NiMoP and Zeolite Catalysts, Si Selection In the same manner as the previous example, 40 grains of two families of catalysts were subjected to the LIBS analysis. It is a co1: 2lyseur supported on alumina type NiMoP. The second catalyst is a zeolite catalyst essentially containing a zeolite ZSM5 and an aluminum binder, and contains between 30 and 40% Si. The LIBS system used is equipped with a laser (Centurion, 1064 nm, 100 Hz) and a spectrometer with a high frequency of acquisition (HR2000 +, grating at 1200 lines / mnn, resolution of 0.18 nm for the zone 180-350 nrn). The sorting was carried out on the basis of the presence or absence of the Si line at 280.308 nm, a signal of more than 20000 hits being visible when the catalyst grain is a catalyst containing zeolite. The LIBS technique makes it easy to differentiate a batch of catalysts containing a mixture of NiMoP / alumina and zeolitic catalyst,
    权利要求:
    Claims (5)
    [0001]
    REVENDICATIONS1. Process for separating at least one catalyst or adsorbent from a homogeneous mixture of catalysts and / or adsorbents, said catalysts or adsorbents having been used in a process for treating gas or hydrocarbon feedstock, in which process the grains of catalysts or adsorbents are separated according to a sorting threshold corresponding to a content of the constitutive element sought and defined by the operator, in which process - the catalyst particles of said mixture pass a detection system LIBS which detects the length of waveform characterizing said constituent element, the analyzer associated with the LIBS processes the signal sent by the detection system by comparing it with a significant reference value of the sorting threshold, the analyzer sends a signal to control the evacuation of the grains according to its content in said element and at least two batches are obtained: at least one batch of catalysts heavily loaded with said cement at the sorting threshold and at least one batch of catalysts that are lightly loaded into said element with respect to the sorting threshold; and at least one of the catalyst batches that are lightly loaded with said element is recycled in the gas treatment process or hydrocarbon feed after a possible regeneration.
    [0002]
    2 - Process according to claim 1 wherein the sorting threshold is 0`) / 0.
    [0003]
    3 'Method according to one of the preceding claims, wherein the catalyst to be separated contains as a constituent element a non-metallic element, preferably selected from the group consisting of P, B. Si, Li, Na, K, Ca, Cl .
    [0004]
    4. Method according to one of the preceding claims, wherein the catalyst to be separated contains as constitutive element Cr, Cu, Al, Ti, Zn.
    [0005]
    5. Method according to one of the preceding claims, wherein the hydrocarbon feedstock treatment process is selected from the group formed by hydrotreating, hydrocracking, dehydrogenation, hydroconversion of distillates, hydrogenation, Isomerization, reforming and gas treatment is chosen from the group formed by the Claus process and tail gas treatments. The process as claimed in claim 1, in which the catalysts are used hydrotreating and / or hydrocracking catalysts, the support of which is composed of alumina or silica-alumina with the possible presence of zeolite. 7 - Process according to one of the preceding claims, wherein the catalysts are in a homogeneous form, preferably in the form of cylindrical extrudates, beads, trilobes or multilobes. 8 - Method according to one of the preceding claims, wherein the number of grains detected / analyzed being at least 100 per second for a detection time of less than 10m ... s. 10 - Method according to one of the preceding claims, wherein the spacing between the grains is equal to or less than the average grain length. 1D- Method according to one of the preceding claims, wherein the sorting threshold for P is between 1 and 2% weight P. 11 - Method according to one of the preceding claims, wherein the sorting threshold for B 15 is between 0.5 and 2% by weight of B 12 'Process according to one of the preceding claims, wherein the sorting threshold for Cr is between 3 and 6% by weight Cr. 13 - Method according to one of the preceding claims, wherein the sorting threshold for Si is between 1 to 3% by weight. 14 - Method according to one of the preceding claims, wherein the sorting threshold for Na is between 0.5 to 2% by weight.
    类似技术:
    公开号 | 公开日 | 专利标题
    EP3302798B1|2020-01-15|Method for the compositional sorting of catalysts or adsorbents in mixtures of catalysts and/or adsorbents
    WO2015082424A1|2015-06-11|Method for sorting spent catalyst depending on the metals of the catalyst
    US8476545B2|2013-07-02|Sorting pieces of material based on photonic emissions resulting from multiple sources of stimuli
    CN108136445B|2020-11-20|Material sorting system
    US8307985B2|2012-11-13|Colour sorting of catalyst or adsorbent particles
    AU655964B2|1995-01-19|Classifying or sorting
    JP5724067B2|2015-05-27|Method and apparatus for sorting potato products
    PT2198983E|2011-12-13|Method for separating mineral impurities from calcium carbonate-containing rocks by x-ray sorting
    EP2064004B1|2011-01-26|Sequential selective sorting method and installation for implementing it
    EP3302797B1|2020-01-15|Method for sorting contaminated catalysts or adsorbents
    WO2017024035A1|2017-02-09|Metal analysis during pharmaceutical manufacturing
    US8436268B1|2013-05-07|Method of and apparatus for type and color sorting of cullet
    EP3352919B1|2019-01-02|System and method for analyzing and sorting material
    WO2017108378A1|2017-06-29|Method for converting petroleum feedstocks comprising a step of ebullated-bed hydrocracking incorporating a catalyst sorting system
    EP3160642B1|2018-04-18|Method for limiting the emission of dust from catalyst grains
    EP3405297B1|2020-03-04|A method and apparatus for sorting tires
    DE102018210015B4|2020-04-02|Device and method for sorting powdery, particulate, granular or lumpy material
    WO2008124925A1|2008-10-23|Fusarium detection method
    EP2782685A1|2014-10-01|Method and system for identifying and separating wood for recycling
    Meirhofer et al.2012|Processing options of heavy fractions from MBT plants
    同族专利:
    公开号 | 公开日
    EP3302798B1|2020-01-15|
    WO2016193479A1|2016-12-08|
    EP3302798A1|2018-04-11|
    US10828632B2|2020-11-10|
    FR3036981B1|2019-04-19|
    DK3302798T3|2020-04-06|
    US20180161767A1|2018-06-14|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US20090000992A1|2007-06-29|2009-01-01|Pierre Dufresne|Colour sorting of catalyst or adsorbent particles|
    WO2015082424A1|2013-12-06|2015-06-11|IFP Energies Nouvelles|Method for sorting spent catalyst depending on the metals of the catalyst|
    US4347121A|1980-10-09|1982-08-31|Chevron Research Company|Production of lubricating oils|
    US8063261B2|2002-01-14|2011-11-22|Sud-Chemie Inc.|Multi-layered dehydrogenation catalyst system and process of use|
    US20140260801A1|2011-07-28|2014-09-18|Technological Resources Pty. Limited|Sorting mined material|JP6653511B2|2016-07-15|2020-02-26|国立研究開発法人産業技術総合研究所|LIBS type object sorting device|
    RU2020109773A3|2017-08-09|2021-11-22|
    US11136511B2|2019-05-23|2021-10-05|Evonik Operations Gmbh|Reactivated hydroprocessing catalysts for use in sulfur abatement|
    CN113021662B|2021-02-26|2022-01-11|苏州银锐环保材料有限公司|Method for accelerating biodegradation of plastic|
    法律状态:
    2016-06-07| PLFP| Fee payment|Year of fee payment: 2 |
    2016-12-09| PLSC| Publication of the preliminary search report|Effective date: 20161209 |
    2017-06-22| PLFP| Fee payment|Year of fee payment: 3 |
    2018-06-27| PLFP| Fee payment|Year of fee payment: 4 |
    2020-06-26| PLFP| Fee payment|Year of fee payment: 6 |
    2021-06-25| PLFP| Fee payment|Year of fee payment: 7 |
    优先权:
    申请号 | 申请日 | 专利标题
    FR1555165|2015-06-05|
    FR1555165A|FR3036981B1|2015-06-05|2015-06-05|PROCESS FOR THE COMPOSITIONAL SORTING OF CATALYST OR ADSORBENT IN MIXTURES OF CATALYSTS AND / OR ADSORBENTS|FR1555165A| FR3036981B1|2015-06-05|2015-06-05|PROCESS FOR THE COMPOSITIONAL SORTING OF CATALYST OR ADSORBENT IN MIXTURES OF CATALYSTS AND / OR ADSORBENTS|
    PCT/EP2016/062725| WO2016193479A1|2015-06-05|2016-06-03|Method for the compositional sorting of catalysts or adsorbents in mixtures of catalysts and/or adsorbents|
    EP16730728.9A| EP3302798B1|2015-06-05|2016-06-03|Method for the compositional sorting of catalysts or adsorbents in mixtures of catalysts and/or adsorbents|
    US15/579,398| US10828632B2|2015-06-05|2016-06-03|Method for compositional sorting of catalyst or adsorbent in mixtures of catalysts and/or adsorbents|
    DK16730728.9T| DK3302798T3|2015-06-05|2016-06-03|PROCEDURE FOR COMPOSITION SORTING OF CATALYSTS OR ADSORBENTS IN BLENDS OF CATALYSTS AND / OR ADSORBENTS|
    [返回顶部]