CN102292418A - Process for hydrodesulfurization, hydrodenitrogenation, hydrofinishing, or amine production - Google Patents

Abstract

Herein disclosed is a method for hydrodesulfurization, hydrodenitrogenation, hydrofinishing, amine production or a combination thereof. The method comprises forming a dispersion comprising hydrogen-containing gas bubbles dispersed in a liquid feedstock, wherein the bubbles have a mean diameter of less than about 5 [mu]m and wherein the feedstock comprises a mixture of petroleum-derived hydrocarbons and a naturally derived renewable oil. The feedstock comprises hydrocarbons selected from the group consisting of liquid natural gas, crude oil, crude oil fractions, gasoline, diesel, naphtha, kerosene, jet fuel, fuel oils, and combinations thereof. The method further comprises contacting the dispersion with a catalyst that is active for hydrodesulfurization, hydrodenitrogenation, hydrofinishing, amine production, or a combination thereof. The catalyst comprises homogeneous catalysts and heterogeneous catalysts. The catalyst may be utilized in fixed-bed or slurry applications.

Description

Be used for the method that hydrogenating desulfurization, hydrodenitrification, hydrofining or amine are produced

Technical field

Generally speaking, hydrogenating desulfurization, hydrodenitrification, amine production and/or the two key that the present invention relates in the liquid stream is saturated.More particularly, the present invention relates to be used to improve hydrogenating desulfurization, hydrodenitrification, amine production and/or the saturated high shear process of two key of liquid stream.

Background technology

Hydrotreatment is meant various catalytic hydrogenation process.Known hydrotreatment comprises hydrogenating desulfurization, hydrodenitrification and hydrodemetallation (HDM), the oil that wherein charging is for example contained residue contacts under the condition of High Temperature High Pressure and hydrogen existence with catalyzer, so that the sulphur constitutional changes are become hydrogen sulfide, the nitrogen component changed ammonification and with metal deposition (usually as sulfide) on catalyzer.

About the up-to-date management expectancy of fuel, diesel oil and sulfur in gasoline level, produced bigger demand to more effective desulfurization means.The charging of experience hydrotreatment, its scope are from the petroleum naphtha to the vacuum resid, and product is used as environmentally acceptable clean fuel in great majority are used.

The hydrotreatment operation is characterised in that opposite with for example hydrocracking, and molecular dimension distributes and do not change basically.Hydrogenating desulfurization (HDS) is a subclass of hydrotreatment, wherein uses the catalytic chemistry process for example to remove desulfuration gasoline or volatile oil, rocket engine fuel, kerosene, diesel oil fuel and the oil fuel from Sweet natural gas and refining petroleum product.The purpose of removing desulfuration is the discharging that reduces by using fuel as the carrier vehicle supplying energy or the caused oxysulfide of burning that acts as a fuel.In petroleum refining industry, the HDS device is also referred to as hydrotreater usually.In the hydrogenating desulfurization of routine, in the presence of High Temperature High Pressure and catalyzer, carbon containing fluid and hydrogen are handled.Sulphur is reduced into H2S gas, and it can be oxidized to elementary sulfur by for example Kraus process then.

Although from strengthening the angle of sulphur technical specification, hydrogenating desulfurization (HDS) can have more and more important effect, hydrodenitrification (HDN) is that hydrocarbon stream also can experience so that be the another kind of process that effective subsequently escalation process is prepared.By for example two keys being carried out saturated hydrocarbon stream being carried out hydrofining or finishing, also be a kind of important escalation process, particularly for the alicyclic hydrocarbon logistics.

Except in order to prevent to pollute the sulphur removal, may make under the situation of downstream processing poisoning of catalyst in the existence of sulphur, also want sulphur removal.For example, when the catalytic reforming unit at the octane value that is used for increasing naphtha stream uses precious metal catalyst (for example platinum and/or ruthenium catalyst), can from naphtha stream, remove desulfuration.

The method and system that is used for removing from the carbon containing fluid sulfocompound before many may be expensive, may comprise harsh reaction conditions, may be not enough to remove the sulfocompound of significant quantity, may not effectively remove sulfocompound, and/or may the scale of being not easy be amplified to big fluid volume with some chemical structure.

Therefore, in industry,, exist demand for improving one's methods of the hydrogenating desulfurization that is used for the carbon containing fluid stream, hydrodenitrification, hydrofining and/or amine production.

Summary of the invention

Herein disclosed is the method that is used for hydrogenating desulfurization, hydrodenitrification, hydrofining, amine production or its combination.In embodiments, method comprises forming and contains the dispersion that is dispersed in the hydrogeneous bubble in the liquid feeding, and wherein bubble has the mean diameter less than about 5 μ m, and wherein charging comprises the mixture of the renewable oils of petroleum derivation hydro carbons and natural origin.

In some cases, charging comprises the hydro carbons that is selected from natural gas liquids, crude oil, crude oil fractions, gasoline, diesel oil, petroleum naphtha, kerosene, rocket engine fuel, oil fuel and combination thereof.In embodiments, form dispersion comprise the mixture that makes hydrogen-containing gas and liquid feeding stand to be higher than about 20, the shearing rate of 000s-1.In certain embodiments, forming dispersion comprises hydrogen-containing gas is contacted in high-shear device with liquid feeding, wherein high-shear device comprises at least one rotor, and wherein in the dispersion forming process at least one rotor with 22.9m/s at least (4, tip speed rotation 500ft/min).In some cases, high-shear device produce at the tip of at least one rotor at least about 1034.2MPa (150, local pressure 000psi).In some cases, the energy expenditure of high-shear device is higher than 1000W/m ³

In another embodiment, method also comprise with dispersion with hydrogenating desulfurization, hydrodenitrification, hydrofining, amine production or its made up activated catalyzer contact.In various embodiments, catalyzer comprises homogeneous catalyst and heterogeneous catalyst.In various embodiments, catalyzer is applied in fixed bed applications or the slurry application.In various embodiments, catalyzer comprises the metal that is selected from cobalt, molybdenum, ruthenium, platinum, palladium, rhodium, nickel, copper, tungsten and combination thereof.

This paper also discloses and has been used for the method that hydrogenating desulfurization, hydrodenitrification, hydrofining or amine are produced.Described method comprises makes the fluid mixture that comprises hydrogen-containing gas and liquid feeding stand to be higher than 20 in high-shear device, 000s ^-1Shearing rate, to produce the dispersion of hydrogen in liquid continuous phase, wherein liquid feeding comprises the mixture of the renewable oils of petroleum derivation hydro carbons and natural origin; And dispersion imported in the fixed-bed reactor, remove reactor product from described fixed-bed reactor, wherein fixed-bed reactor comprise the catalyzer that is effective to hydrogenating desulfurization, hydrodenitrification, hydrofining, amine production or its combination.

In certain embodiments, method also comprises reactor product is separated into gas stream and comprises the liquid product stream of sweetening liq product; From gas stream, remove hydrogen sulfide, produce poor hydrogen sulfide logistics; And the poor hydrogen sulfide logistics of at least a portion is re-circulated to high-shear device.In certain other embodiments, method also comprises the sweetening liq product is reformed.In other embodiments, method also comprises from the product liquid recovery hydrogen of reforming, and is circulated to the hydrogen that a few part reclaims again.In various embodiments, catalyzer comprises the metal that is selected from cobalt, molybdenum, ruthenium, platinum, palladium, rhodium, nickel, copper, tungsten and combination thereof.

In other embodiments, a kind of method is disclosed, described method comprises hydrogen is dispersed in the fluid mixture that comprises liquid feeding to produce the dispersion of hydrogen in liquid feeding external phase that wherein liquid feeding comprises the mixture of the renewable oils of petroleum derivation hydro carbons and natural origin in high-shear device; And in dispersion, importing the catalyst pulp that comprises catalyzer, described catalyzer is for hydrogenating desulfurization, hydrodenitrification, hydrofining, amine production or its combination effectively.

In some cases, catalyzer comprises the metal that is selected from platinum, palladium, rhodium, ruthenium and combination thereof.In some cases, catalyzer comprises the metal that is selected from nickel, copper and combination thereof.In some cases, catalyzer comprises the metal that is selected from cobalt, nickel, ruthenium, copper, palladium, platinum and combination thereof.In some cases, catalyzer comprises the metal that is selected from cobalt, molybdenum, nickel, tungsten and combination thereof.

In addition, the high shear process that is used to improve hydrogenating desulfurization, hydrodenitrification, hydrofining or amine production is disclosed.According to some embodiment, the method of hydrogenating desulfurization, hydrodenitrification, hydrofining or its combination has been proposed, described method comprises that formation comprises the dispersion that is dispersed in the hydrogeneous bubble in the liquid feeding, wherein bubble has the mean diameter less than 5 μ m, and wherein charging comprises petroleum derivation hydro carbons and the mixture that is selected from least a oil of plant oil (plant oil) and vegetables oil (vegetable oil).In embodiments, at least a portion sulfocompound in the liquid phase is reduced the formation hydrogen sulfide.In embodiments, at least a portion nitrogenous compound in the liquid phase is transformed into ammonia.In embodiments, at least a portion unsaturation carbon-to-carbon double bond in the hydrocarbon by hydrogenation by saturated.High shear mixing provides time, the temperature and pressure condition that is reinforced potentially, causes the acceleration chemical reaction between the heterogeneous reaction thing.Bubble can have the mean diameter less than 1.5 or 1 μ m.In embodiments, bubble has the mean diameter that is no more than 400nm.Liquid phase can comprise the hydro carbons that is selected from natural gas liquids, crude oil, crude oil fractions, gasoline, diesel oil, petroleum naphtha, kerosene, rocket engine fuel, oil fuel and combination thereof.In application, charging comprises at least a plant oil or vegetables oil.Vegetables oil can be a soybean oil.

Form dispersion can comprise the mixture that makes hydrogen-containing gas and liquid feeding stand to be higher than about 20,000s ^-1Shearing rate.Forming dispersion can comprise hydrogen-containing gas is contacted in high-shear device with liquid feeding, wherein high-shear device comprises at least one rotor, and wherein in the dispersion forming process, at least one rotor with 22.9m/s at least (4, tip speed rotation 500ft/min).High-shear device can produce at the tip of at least one rotor at least about 1034.2MPa (150, local pressure 000psi).In embodiments, the energy expenditure of high-shear device is higher than 1000W/m ³

Method can also comprise with dispersion with hydrogenating desulfurization, hydrodenitrification, hydrofining or its made up activated catalyzer contact.Catalyzer can comprise the metal that is selected from cobalt, molybdenum, ruthenium and combination thereof.

Also disclose and be used for the method that hydrogenating desulfurization, hydrodenitrification, hydrofining or amine are produced, described method comprises makes the fluid mixture that contains hydrogen-containing gas and comprise the liquid feeding of sulfur component, nitrogen component, unsaturated link(age) or its combination, externally stand to be higher than 20 in the high-shear device, 000s ^-1Shearing rate, to produce the dispersion of hydrogen in liquid continuous phase, wherein liquid feeding comprises the mixture of petroleum derivation hydro carbons and at least a plant oil or vegetables oil, and dispersion imported fixed bed, remove reactor product from described Solid Bed, wherein fixed-bed reactor comprise the catalyzer that is effective to hydrogenating desulfurization, hydrodenitrification, hydrofining or its combination.In application, liquid feeding comprises at least a vegetables oil.Vegetables oil can stem from soybean, palm, castor-oil plant, vegetable seed (canola) and can obtain other crops of oil from it.

Method also comprises reactor product is separated into gas stream and comprises the liquid product stream of sweetening liq product; From gas stream, remove hydrogen sulfide, produce poor hydrogen sulfide logistics; And the poor hydrogen sulfide logistics of at least a portion is re-circulated to external high shear device.Method can also comprise reforms to the sweetening liq product.Can be from the reformation recover hydrogen, and the hydrogen that at least a portion reclaims can be circulated again.The mean air bubble diameter of bubble hydrogen can be less than about 5 μ m in the dispersion.Dispersion under atmospheric pressure can be stablized at least about 15 minutes.On fluid, use shearing and can comprise the high-shear device that the fluid importing is contained at least two producers.

The time that is more suitable for, the temperature and pressure condition that compares otherwise may provide is provided some embodiment of above-described method potentially, and it has increased the speed of heterogeneous method potentially.The product that some embodiment of above-described method increases by the catalyzer that moves, provides per unit consumption under low temperature and/or pressure, minimizing reaction times and/or reduction capital construction and/or running cost provide the reduction of overall cost potentially.These and other embodiment and potential advantage will be apparent in the detailed description and the accompanying drawings below.

Some other embodiment has dynamic commercial applications potentially, and the material that can be used in many industry is provided.Application of the present invention can be used the different hydroprocessing processs that are used in combination with various devices, so that form the system that allows to carry out more effective and heterogeneous reaction when these materials are exposed to some catalyzer.These systems may need less construction and operation capital.In addition, as the result of these system and methods, product yield may increase.Alternatively, if the product yield of existing method can be accepted, reduce required residence time permission and use temperature and/or the pressure lower than ordinary method.

In some optional application, can on some byproduct material (sulphur, nitrogen etc.) of the method and system of discussing at present, carry out further hydroprocessing technique.For example, nitrogen is used to form nitroaromatic.The hydrogenation of nitroaromatic or shortening are used to produce aromatic amine.Many commercialization reactions that are used to produce these amine have utilized the gas phase hydrogenation of nitroaromatic.Amine is known to have wide variety of functions, for example as organic solvent, agrochemicals, medicine, tensio-active agent etc.

Description of drawings

In order to describe the preferred embodiments of the invention in more detail, referring now to the figure that encloses, wherein:

Fig. 1 is according to embodiment of the present disclosure, comprises the synoptic diagram of outside high-shear dispersive heterogeneous reaction system.

Fig. 2 is according to another embodiment of the present disclosure, comprises the synoptic diagram of outside high-shear dispersive heterogeneous reaction system.

Fig. 3 is the longitudinal cross-section figure of the multistage high-shear device that uses in the embodiment of system.

Fig. 4 is the schematic representation of apparatus that is used for the hydrodesulfurizationprocess process of embodiment 1.

Fig. 5 is according to embodiment of the present disclosure, uses high-shear device to carry out the synoptic diagram of the system of amine production.

Representation and name

When using in this article, term " dispersion " is meant that comprising at least two kinds of being not easy to mix with being dissolved in together can distinguish the material liquified mixt of (or " mutually ").When using in this article, " dispersion " comprises " continuously " phase (or " matrix "), and it accommodates discontinuous drop, bubble and/or the particle of other phases or material therein.Therefore, the term dispersion can be meant and comprise the foam that is suspended in the bubble in the liquid continuous phase, the drop of first kind of liquid is whole to be dispersed in emulsion in the external phase that comprises with first kind of immiscible second kind of liquid of liquid and the wherein whole continuous liq phase that is distributed with solid particulate.When using in this article, term " dispersion " comprises the alveolate continuous liq phase of wherein whole distribution, wherein wholely is distributed with the continuous liq phase of solid particulate (for example solid catalyst), the external phase of first kind of liquid of the whole drop that is distributed with the second kind of liquid that is insoluble to external phase basically wherein, and the wherein whole liquid phase that is distributed with any or combination of solid particulate, immiscible liquid drop and bubble.Therefore, dispersion can be used as homogeneous mixture (for example liquid/liquid phase) in some cases or exists as non-homogeneous mixture (for example gas/liquid, solid/liquid or gas/solid/liquid), and this is according to the difference of the character of the material that is selected for combination and different.

In the disclosure, term " renewable oils of natural origin " (NDRO) stems from vegetables oil or animal tallow or its combination, and comprises triglyceride level, stems from the lipid acid of triglyceride level, the esterification that stems from triglyceride level or transesterification lipid acid or its combination.The example of transesterification lipid acid is a biofuel.

Describe in detail

General introduction

The speed that comprises liquid, gas and solid chemical reaction is different and different according to duration of contact, temperature and pressure.In hope with two or more homophase (for example, solid and liquid not; Liquid and gas; Solid, liquid and gas) the starting material situation of reacting under, one of limiting factor of control speed of reaction is the duration of contact of reactant.Under the situation of heterogeneous catalytic reaction, exist other rate-limiting factors, be about to reacted product and remove to allow other reactants of catalyst from catalyst surface.Usually control by mixing the duration of contact of reactant and/or catalyzer, and described mixing provides the contact that participates in two or more reactants of chemical reaction.

The reactor assemblies that comprises external high shear device or mixing tank as described herein can reduce mass transfer limitations, therefore allows reaction more near kinetic limitation.When speed of reaction increases, can reduce the residence time, thereby increase obtainable flux.As the result of high shear system and method, product yield may increase.Alternatively,, reduce the required residence time, can allow to use temperature and/or the pressure lower than ordinary method by introducing suitable high-shear if the product yield of existing method can be accepted.

In addition, without wishing to be bound by theory, it is believed that by the shear conditions that reactor assemblies provided that comprises external high shear device as herein described or mixing tank, can allow under regular situation, will can not carried out hydrogenating desulfurization under the overall operation condition with any significance degree generation by anticipation reaction.Although the discussion to system and method will be made with reference to hydrogenating desulfurization, should be appreciated that disclosed system and method also is applicable to the hydrodenitrification and the hydrofining of hydrocarbon stream.Although be called as " hydrocarbon " or " carbon containing " logistics, charging (as what further discuss hereinafter) can comprise the mixture of petroleum derivation hydro carbons and plant oil or vegetables oil.

The system that is used for hydrogenating desulfurization.Describe high-shear hydrogenating desulfurization system referring now to Fig. 1, it is the process flow sheet of embodiment of high shear system 1 that is used to comprise the fluidic hydrogenating desulfurization of S-contained substance.The basic module of representative system comprises external high shear device (HSD) 40, container 10 and pump 5.As shown in fig. 1, high-shear device 40 is positioned at Vessel/reactor 10 outsides.Every kind of these assembly is described in greater detail below.Pipeline 21 links to each other with pump 5, is used to import liquid feeding, for example comprises the carbon containing fluid of sulfocompound.Pipeline 13 links to each other pump 5 with HSD 40, and pipeline 18 links to each other HSD 40 with container 10.Pipeline 22 can link to each other with pipeline 13, is used to import hydrogen-containing gas (H for example ₂).Alternatively, pipeline 22 can link to each other with the inlet of HSD 40.Pipeline 17 can link to each other with container 10, is used to remove unreacted hydrogen, hydrogen sulfide product and/or other reactant gasess.If desired, between container 10 and HSD 40 or in the front of pump 5 or HSD 40, can comprise other assemblies or processing step, as after the explanation of having read the high-shear hydrodesulfurizationprocess process of hereinafter describing, becoming tangible.For example, if desired, pipeline 20 can link to each other with pipeline 21 or the pipeline 13 from downstream position (for example from container 10), to provide repeatedly by operation.

High-shear hydrogenating desulfurization system can also comprise the downstream processing device, by removing hydrogen sulfide in its product from container 10.Fig. 2 is the synoptic diagram of high-shear hydrogenating desulfurization system 300 according to comprising of another embodiment of the present disclosure of outside high-shear diverting device 40.In the embodiment of Fig. 2, high-shear hydrogenating desulfurization system 300 goes back contained gas separator vessel 60, hydrogen sulfide absorption device 30 and the stripping distillation tower 70 that boils again.

In embodiments, high-shear desulphurization system also is included in the gas separator container in container 10 downstreams.Gas separator container 60 can comprise be used at least a portion from the inlet of the product that comprises hydrogen sulfide and carbonaceous liquid of container 10, the outlet line 44 and being used for that is used to comprise the gas stream of hydrogen sulfide removes the gas separator liquid exit line 49 of the liquid of sulfocompound.

High-shear hydrogenating desulfurization system 300 can also comprise resorber 30.Resorber 30 can comprise be used for through outlet line 44 discharge at least a portion gas stream of gas separators 60 inlet, be used for the inlet 47 of poor amine logistics, the outlet line 54 of gas after being used for the outlet 48 of rich amine logistics and being used for removing the cleaning of hydrogen sulfide.Pipeline 45 can be communicated with by device outlet gas line 44 fluids separated from the gas, and can be used for the hydrogen sulfide containing gas of a part is imported gas separator outlet line 44, is used for further processing.Pipeline 53 can import resorber outlet gas line 54 with the gas after the part cleaning, is used for further processing.Pipeline 17 can import resorber outlet line 54 with the gas after the part cleaning, turns back to high-shear device 40.For example, pipeline 17 can be communicated with pipeline 41 fluids that contain fresh hydrogen-containing gas, thus to disperseing 22 chargings of hydrogen-containing gas pipeline.

High shear system 300 can also comprise distillation tower 70.Distillation tower 70 can be the stripping distillation tower that for example boils again.Water distilling apparatus 70 comprises the inlet that is communicated with gas separator liquid exit line 49 fluids from gas separator 60, be used for the outlet 51 of the low product logistics of boiling and be used to comprise the outlet 52 of the product liquid of the carbonaceous liquid of having removed sulfocompound.Outlet 51 can be communicated with pipeline 45 fluids.

High-shear hydrogenating desulfurization system 300 can also comprise heat exchanger 80, and it can be positioned on the outlet line 16 of container 10, and can be used for the thermal response product that container 10 is left in the part cooling.In some applications, heat exchanger 80 also can be used for the reactor feed in the pipeline 21 is preheated.Heat exchanger 80 can be a for example water cooling formula.In embodiments, the reactor product of the heat exchange in the outlet line 42 has experienced the pressure reduction.Pressure reduces and can implement by pressure controller 50.In embodiments, outlet line 42 is communicated with heat exchanger 80 and pressure controller 50 fluids.PC 50 can reduce the hydrodynamicpressure in the outlet line 42 to about 303.9kPa-506.6kPa (3 to 5 normal atmosphere).Outlet line 43 devices 60 separated from the gas and pressure controller 50 fluids from pressure controller 50 are communicated with.Leave the mixture of the liquids and gases of pressure controller 50 through outlet line 43, can under the absolute pressure of for example about 35 ℃ and 303.9kPa-506.6kPa (3 to 5 normal atmosphere), enter gas separator container 60.

High shear device.External high shear device (HSD) 40 is also sometimes referred to as high-shear device or high shear device, is configured to receive by pipeline 13 contain the carbon containing fluid that comprises sulfocompound and the inlet logistics of molecular hydrogen.Alternatively, HSD 40 can be configured to receive liquid and gaseous state reactant stream by source line (not shown) independently.Although in Fig. 1, only shown a high-shear device, should be appreciated that some embodiment of system can have two or more high shear device of arranging in serial or parallel connection mobile mode.HSD 40 has utilized one or more mechanisms that contain the producer of rotor/stator sets, and each producer has the gap between stator and rotor.The rotor of each producer group and the gap between the stator can be fixed, also can be adjustable.In certain embodiments, can use two or more rotor configurations to strengthen shearing, wherein inner rotator and external rotor rotate in the opposite direction.Similar with single rotor/stator device, external rotor is also in the face of stator.Having mechanical complexity and the maintenance subsequently that the high-shear device of a plurality of reverse rotation rotors has increases, and makes them the most useful when needs are extremely sheared.HSD 40 is configured to produce the bubble of submicron or micro-meter scale in flowing through the reaction-ure mixture of high-shear device.High-shear device contains casing or support, so that can control the pressure and temperature of reaction mixture.

In general, according to the ability of high shear device mixed stream, they can be divided into three kinds of main types.Mixing is the process that reduces the size of particle in the fluid or heterogeneous material.A kind of tolerance of blended degree or adequacy is the energy density that is used to make fluid particle disruptive per unit volume that mixing device produces.Carry out the differentiation of type according to the energy density of delivering.Three classes have enough energy densities, can stably produce particle size in submicron to five ten micrometer ranges mixture or the industrial mixing tank of emulsion comprise homogenization valve, colloidal mill and super mixer.In being called as the first kind high-energy rig of homogenization valve, pending fluid is crossed slit valve by pump under very high pressure, enters in the lower environment of pressure.Stride across the pressure gradient of valve and the turbulent flow and the cavatition of generation and play a role, to break any particle in the fluid.These valve systems the most normally are used for milk homogenization, can produce submicron to the interior average particle size particle size of an about micrometer range.

The other end at energy density spectrum is the 3rd class device that is called as low energy system.These systems have in processed fluidic reservoir usually with the blade or the fluid rotor of high speed rotating, and its more common many application is food articles.These low power range systems are used for traditionally in processed fluid can be accepted situation greater than 20 microns mean particle size.

According to being shipped to fluidic mixed tensor density, between low energy system and homogenization valve is colloidal mill and high shear force rotor-stator device, and they are classified as the moderate energy device.The structure of typical colloidal mill comprises conical or discoid rotor, it with the stator of complementary, liquid cooling between separated by closely-controlled rotor-stator gap, this gap is arrived between the 10.16mm (0.001-0.40 inch) at 0.0254mm usually.Rotor is passed through directly to drive or the belt Mechanical Driven by electro-motor usually.When rotor during with high speed rotating, between the outside surface and inner surface of stator of rotor, the shearing force convection cell that produces in the gap is processed with the fluid pump for it.The colloidal mill of many suitable adjustment can produce the average particle size particle size of 0.1-25 micron in processed fluid.These abilities make colloidal mill be suitable for various application, comprise the processing of colloid and oil/water-base emulsion, and for example makeup, mayonnaise or silicone/silver amalgam form the processing of required emulsion, to the mixing of roofing flux.

Tip speed be the unit time internal rotor the tip the periphery distance of process.Therefore, tip speed is the function of rotor diameter and rotation frequency.Tip speed (unit by for example rice/minute) can by with rotor tip process periphery distance 2 π R, wherein R be rotor radius (unit for for example meter), (unit rpm) calculates for for example rev/min to multiply by the frequency of rotation.Colloidal mill can have the tip speed that for example surpasses 22.9m/s (4500ft/min), and can surpass 40m/s (7900ft/min).For the purpose of this disclosure, term " high-shear " is meant that tip speed can surpass 5.1m/s (1000ft/min) and need exterior mechanical to drive electric device with the mechanical rotor stator apparatus (for example colloidal mill or rotor-stator decollator) of energy drives in the logistics of question response product.For example, in HSD40, can obtain to surpass the tip speed of 22.9m/s (4500ft/min), and tip speed can surpass 40m/s (7900ft/min).In certain embodiments, HSD 40 can deliver 300L/h at least with the tip speed of 22.9m/s (4500ft/min) at least.Watt consumption can be about 1.5kW.HSD 40 is combined with very little shear gap with high tip speed, has produced significant shearing force on processed material.The amount of shearing force will depend on fluidic viscosity.Therefore, in the high-shear device operational process, produced the regional area that pressure and temperature raises in rotor tip.In some cases, local elevated pressure be about 1034.2Mpa (150,000psi).In some cases, the local temperature that raises is about 500 ℃.In some cases, these partial pressure and temperatures raise and can continue number nanosecond or number psec.

The approximation (kW/L/min) that is input to the energy in the fluid can be estimated by measuring motor energy (kW) and fluid output (L/min).As above-mentioned, tip speed is the speed (ft/min or m/s) relevant with the end of the one or more spinner members that produced the mechanical force that puts on reactant.In embodiments, the energy expenditure of HSD40 is greater than 1000W/m ³In embodiments, the energy expenditure of HSD 40 is at about 3000W/m ³To about 7500W/m ³Scope in.

Shearing rate is that tip speed is divided by shear gap width (minimum clearance between rotor and the stator).The shearing rate that produces in HSD40 can be greater than 20,000s ^-1In certain embodiments, shearing rate is at least 40,000s ^-1In certain embodiments, shearing rate is at least 100,000s ^-1In certain embodiments, shearing rate is at least 500,000s ^-1In certain embodiments, shearing rate is at least 1,000,000s ^-1In certain embodiments, shearing rate is at least 1,600,000s ^-1In embodiments, the shearing rate that HSD40 produces is 20,000s ^-1To 100,000s ^-1Scope in.For example, in an application, rotor tip speed is about 40m/s (7900ft/min), and shear gap width is 0.0254mm (0.001 inch), and the shearing rate of generation is 1,600,000s ^-1In Another application, rotor tip speed is about 22.9m/s (4500ft/min), and shear gap width is 0.0254mm (0.001 inch), and the shearing rate of generation is about 901,600s ^-1

HSD 40 can or be transported to the hydrogen high dispersing and comprise in the main liquid phase of carbon containing fluidic (external phase), described carbon containing fluid under normal circumstances, the sulfocompound in making at least a portion hydrogen and carbon containing fluid reacts under the condition of the product logistics that comprises hydrogen sulfide with generation, with the hydrogen unmixing.In embodiments, the carbon containing fluid also comprises catalyzer mutually.In certain embodiments, HSD 40 comprises colloidal mill.The colloidal mill that is fit to is by for example IKA

Works, (Wilmington, NC) with APV North America, (Wilmington MA) makes Inc. Inc..In some cases, HSD 40 comprises IKA

Works, the DispaxReactor of Inc.

High-shear device contains at least one spinner member, and it produces the mechanical force that puts on reactant.High-shear device contains at least one stator and at least one stator, their certain intervals of being separated by.For example, rotor can be conical or discoidal, can separate with the stator of shape complementarity.In embodiments, rotor and stator all contain the tooth that a plurality of peripheries are separated by.In certain embodiments, stator is adjustable, to obtain required shear gap between the rotor of each producer (rotor/stator sets) and stator.Groove between the tooth of rotor and/or stator can replace directed to increase turbulent flow in the alternative level.Each producer can be by any suitable drive systems, and they are configured to the rotation that can provide essential.

In certain embodiments, the minimum clearance between stator and the rotor (shear gap width) at about 0.0254mm (0.001 inch) between about 3.175mm (0.125 inch).In certain embodiments, the minimum clearance between stator and the rotor (shear gap width) is about 1.52mm (0.060 inch).In some structure, the minimum clearance between stator and the rotor (shear gap) is about 1.78mm (0.07 inch).The shearing rate that high-shear device produces can change with lengthwise position along flowpaths.In certain embodiments, rotor is set to the speed rotation to match with the diameter of rotor and required tip speed.In certain embodiments, high-shear device has fixed gap (shear gap width) between stator and rotor.Alternatively, high shear device has adjustable gap (shear gap width).

In certain embodiments, HSD 40 contains single-stage dispersing chamber (being single rotor/stator sets, single producer).In certain embodiments, high shear device 40 is multi-stage in-line decollators, and contains a plurality of producers.In certain embodiments, HSD 40 contains at least two producers.In other embodiments, high shear device 40 contains at least three high shear force producers.In certain embodiments, high shear device 40 is multi-level mixers, therefore shearing rate is (as above-mentioned, its variation that is directly proportional with tip speed, with the variation that is inversely proportional to of rotor/stator clearance width) change with lengthwise position along flowpaths, as what further describe hereinafter.

In certain embodiments, each level of external high shear device has interchangeable mixing tool, and handiness is provided.IKA for example

Works, Inc.Wilmington, NC and APVNorth America, Inc.Wilmington, the DR 2000/4 Dispax Reactor of MA Contain three grades and disperse module.This module can comprise nearly three rotor/stator sets (producer), can select thin, medium, thick and ultra-fine for each level.This allows to produce the dispersion of the narrow distribution with required bubble size (for example bubble hydrogen).In certain embodiments, each level is operated with ultra-fine producer.In certain embodiments, at least one producer group has the minimum rotor/stator clearance (shear gap width) greater than about 5.08mm (0.20 inch).In optional embodiment, at least one producer group has the minimum rotor/stator clearance greater than about 1.78mm (0.07 inch).

With reference now to Fig. 3,, it has shown the longitudinal sectional drawing of the high-shear device 200 that is fit to.The high-shear device 200 of Fig. 3 is the diverting devices that contain three levels or three rotor-stator combinations.High-shear device 200 is the diverting devices that contain three levels or three rotor-stator combinations 220,230 and 240.The rotor-stator combination can be called as producer 220,230,240 or level, is not limited in this respect.Three rotor/stator sets or producer 220,230 and 240 are along drive shaft 250 arranged in series.

First producer 220 contains rotor 222 and stator 227.Second producer 230 contains rotor 223 and stator 228.The 3rd producer 240 contains rotor 224 and stator 229.For each producer, rotor is rotatably driven by input 250, and rotates with arrow 265 indicated directions around axle 260.The direction of rotation can be opposite with the direction that arrow 265 shows (for example around turning axle 260 clockwise or counterclockwise).Stator 227,228 is fixedlyed connected with the wall 255 of high-shear device 200 with 229.

As what above mention, each producer has shear gap width, and it is the minor increment between rotor and the stator.In the embodiments of figure 3, first producer 220 has first shear gap 225; Second producer 230 has second shear gap 235; The 3rd producer 240 has the 3rd shear gap 245.In embodiments, the width of shear gap 225,235,245 at about 0.025mm to the scope of about 10.0mm.Alternatively, method comprises uses high-shear device 200, and the width of its intermediate gap 225,235,245 is at about 0.5mm extremely in the scope of about 2.5mm.In some cases, shear gap width is maintained at about 1.5mm.Alternatively, the width of shear gap 225,235,245 is for producer the 220,230, the 240th, and is different.In some cases, the width of the shear gap 225 of first producer 220 is greater than the width of the shear gap 235 of second producer 230, and the latter is again greater than the width of the shear gap 245 of the 3rd producer 240.As above-mentioned, the producer of each grade can exchange, and handiness is provided.High-shear device 200 can be constructed such that along the direction shearing rate of stream 260 will vertically be increased step by step.

Producer 220,230 and 240 can have thick, medium, thin and the superfine feature.Rotor 222,223 and 224 and stator 227,228 and 229 can have toothed design.Each producer can have two or more groups rotor-stator tooth.In certain embodiments, rotor 222,223 and 224 peripheries at each rotor contain 10 rotor tooths of separating with upper periphery.In embodiments, stator 227,228 and 229 peripheries at each stator contain 10 stator tooths of separating with upper periphery.In embodiments, the internal diameter of rotor is about 12cm.In embodiments, the diameter of rotor is about 6cm.In embodiments, the external diameter of stator is about 15cm.In embodiments, the diameter of stator is about 6.4cm.In certain embodiments, the diameter of rotor is 60mm, and the diameter of stator is 64mm, and the gap of about 4mm is provided.In certain embodiments, each level in three grades is used ultra-fine producer operation, contains the shear gap between about 0.025 to about 4mm.For the application that solid particulate wherein will transport by high-shear device 40, can select the shear gap width (minimum clearance between rotor and the stator) that is fit to, compatibly to reduce particle size and to increase granule surface area.In embodiments, this has and is beneficial to by shearing and discrete particles increases the surface-area of catalyzer.

High-shear device 200 is formed at inlet 205 places and receives reactant stream from pipeline 13.But reaction mixture comprises hydrogen as disperse phase, and comprises liquid feeding as external phase.Feed stream can also comprise the particulate solid catalyst component.The feed stream that enters inlet 205 is crossed producer 220,230, was collapsed 240 then by the order pump, so that form the product dispersion.The product dispersion is left high-shear device 200 by outlet 210 (and pipelines 18 of Fig. 1).The rotor 222,223,224 of each producer with respect to 227,228,229 rotations of fixed stator, provides high shear rate with high speed.The rotation of rotor is fluid feed stream pump admission port 205 for example, outwards by shear gap (and, if present, by the space between the rotor tooth and the space between the stator tooth), produced local shear conditions.On the fluid of (and if present, in the gap between rotor tooth and the stator tooth), process fluid has also produced the product dispersion to high shear in the shear gap 225,235 and 245 that fluid is flowed through.The product dispersion is left high-shear device 200 through high-shear outlet 210 (and pipelines 18 of Fig. 1).

The product dispersion has the average bubble size less than about 5 μ m.In embodiments, HSD 40 produces the dispersion of average bubble size less than about 1.5 μ m.In embodiments, HSD 40 produces the dispersion of average bubble size less than 1 μ m; Under the preferable case, the diameter of bubble is a submicron order.In some cases, average bubble size is from about 0.1 μ m to about 1.0 μ m.In embodiments, HSD 40 produces the dispersion of average bubble size less than about 400nm.In embodiments, HSD 40 produces the dispersion of average bubble size less than 100nm.The dispersion that high-shear device 200 produces, the bubble that wherein comprises can under atmospheric pressure keep disperseing to last at least about 15 minutes.

Without being limited by theory, in emulsion chemistry, known submicron particles or the bubble that is dispersed in the liquid mainly moves by the pedesis effect.Bubble in the product dispersion that high-shear device 200 is produced may have higher mobility when the frictional belt by solid catalyst particle, thereby promotes and quickened catalyzed reaction by the transportation that increases reactant.

In some cases, high-shear device 200 comprises IKA

Works, Inc.Wilmington, NC and APV North America, Inc.Wilmington, the Dispax Reactor of MA Have several models to use, they have various inlet/outlet connection, horsepower, tip speed, output rpm and flow velocity.The flux requirement is depended in the selection of high-shear device, and the desired size that leaves particle in the dispersion in the pipeline 18 (Fig. 1) of outlet 210 of high-shear device 200 or bubble.For example, IKA

DR 2000/4 type, contain belt drives, 4M producer, PTFE wear ring, inlet flange 25.4mm (1 inch) health level clip, discharge flange 19mm (3/4 inch) health level clip, 2HP power, output speed 7900rpm, flow holds the about 300-700L/h of power (water) (according to the difference of producer and different), tip speed 9.4-41m/s (1850ft/min is to 8070ft/min).

Container.Container or reactor 10 are that the container of heterogeneous reaction with any kind of carrying out above-mentioned conversion reaction can take place.For example can use continuous or semicontinuous stirred-tank reactor by serial or parallel connection, or one or more batch reactor.In some applications, container 10 can be a tower reactor, can be tubular reactor or multi-tubular reactor in other are used.It is contemplated that any amount of reactor inlet pipeline, in Fig. 1, shown two (pipelines 14 and 15).Source line can be the catalyst inlet pipeline 15 that links to each other with container 10, is used for receiving catalyst solution or slurry in the system operation process.Container 10 can comprise the vent line 17 that is used to discharge gas, and the outlet product pipeline 16 that is used for the product logistics.In embodiments, container 10 comprises a plurality of reactor product pipelines 16.

Hydrogenation reaction will be in the time that is fit to, generation when the temperature and pressure condition exists.In this sense, if the temperature and pressure condition is suitable, hydrogenation reaction can take place at any some place in the schema of Fig. 1.When using the round-robin slurry catalyst based, reaction more may occur in the site of container 10 outsides of Fig. 1 demonstration.Yet generally Li San reactor/vessel 10 is ideal, to allow to increase the residence time, stirring and heating and/or cooling.When using reactor 10, reactor/vessel 10 can be fixed-bed reactor, fluidized-bed reactor or transport bed reactor, and because the existence of catalyzer and to the influence of hydrogenation speed may become the main positions that hydrogenation takes place.

Therefore, container 10 can be the container that any kind of hydrogenating desulfurization can take place.For example, container 10 can comprise the still formula or the tubular reactor of one or more serial or parallel connections.The reaction of being undertaken by high shear process 1 can comprise that wherein the catalyzer as the another kind of component of reaction mixture is present in the homogeneous catalytic reaction in the phase homophase, or comprises the heterogeneous catalytic reaction of solid catalyst.Randomly, as what discussed among the embodiment 1 hereinafter, by using high-shear device 40, hydrodesulfurization reaction does not use catalyzer to take place.When using container 10, container 10 can be used as the known additive method operation of professional in slurry reactor, fixed-bed reactor, trickle-bed reactor, fluidized-bed reactor, bubble-plate column or present technique field.In some applications, introducing external high shear device 40 will allow for example trickle-bed reactor to be operated as slurry reactor.This may be useful for for example including but not limited to hydrodenitrification, hydrogenating desulfurization and hydrogenation deoxidation reaction.

Container 10 can comprise one or more following parts: stirring system, heating and/or cooling way, pressure-measuring instrument, thermometric instruments, one or more injection points, and regulator of level (not shown) are as knowing at the reaction vessel design field.For example, stirring system can comprise the mixing tank that motor drives.Heating and/or refrigerating unit can comprise for example heat exchanger.Alternatively, because most of in certain embodiments conversion reaction can take place in HSD40, so container 10 may mainly be used as storage vessel in some cases.Although generally not too wish, can omit container 10 in some applications, if particularly a plurality of high shear devices/reactors is connected when using, just as described further below.

Heat exchanger.Except the heating/cooling way of container 10 above-mentioned, in Fig. 1 in the modification of embodiments shown, it is also conceivable that other outside or inner being used to heats or cool off the heat exchanger of process streams.For example, if reaction is heat release, can from container 10, remove reaction heat by the known any method of the professional in present technique field.Also can consider to use indirect heating and/or cooling heat switch.When system 1 during with the operation of load mode repeatedly, some positions that are fit to of one or more such heat exchangers are between pump 5 and the HSD40, between HSD40 and the container 10 and between container 10 and pump 5.Some non-limiting instance of such heat exchanger is shell-type, tubular type, board-like and tube coil type heat exchanger, as known in the art.

Pump.Pump 5 is configured for continuously or semi continuous operation, and can be anyly can produce, be preferably greater than 303.975kPa (3atm) pressure greater than 202.65kPa (2atm) pressure, to allow the pumping unit that be fit to of controlled flow by HSD40 and system 1.For example, (Niles, Dayton pressure multiplier pump 2P372E type IL) is the pump that is fit to for the Roper 1 type toothed gear pump of Roper pump company (Commerce Georgia), Dayton Electric Co.Under the preferable case, all contact parts of pump are by stainless steel, for example 316 stainless steels constitute.In some embodiment of system, pump 5 can produce the pressure that is higher than about 2026.5kPa (20atm).Except pump 5, one or more extra high-pressure pump (not shown)s can be comprised in the system of Fig. 1 demonstration.For example, can comprise between HSD40 and container 10 and pump 5 similar topping-up pumps, the pressure of the container 10 that is used for raising perhaps can place recycle pump on the pipeline 17, and the gas that is used for coming from container 10 is re-circulated to HSD 40.As another example, can comprise and pump 5 similar feed supplement pumps, be used for other reactants or catalyzer are imported container 10.

Produce hydrogen sulfide by the carbon containing fluidic hydrogenating desulfurization that contains sulfocompound.

The operation of high shear system 1 is discussed referring now to Fig. 1.Description will be carried out at hydrogenating desulfurization, but should be appreciated that system can be used for other hydrotreatments, for example hydrodenitrification.In the operation that is used for the fluidic hydrogenating desulfurization, can disperse the hydrogen-containing gas logistics through pipeline 22 import systems 1, and in pipeline 13, merge with liquid feeding.The liquid feeding that can handle by system and method disclosed herein can be various dissimilar.In embodiments, charging comprises carbon, and can be called as the carbon containing fluid.Carbon in the carbon containing fluid can be the part of carbon compound or material.Carbon compound or material can be hydro carbons.The carbon containing fluid can comprise liquid hydrocarbon, such as but not limited to fossil oil, crude oil or crude oil fractions, diesel oil fuel, gasoline, kerosene, light oil, petroleum fractions and combination thereof.The carbon containing fluid of another kind of type comprises liquefaction hydro carbons, for example liquefied petroleum gas (LPG).In embodiments, the carbon containing fluid is a petroleum-based fluids.Liquid stream in the pipeline 13 can comprise, for example, and petroleum naphtha, diesel oil, heavy oil and combination thereof.

In embodiments, liquid feeding comprises the mixture of the oil of petroleum derivation hydro carbons and one or more non-petroleum sourcess.Oil can be selected from for example plant oil, vegetables oil and combination thereof.In application, the mixture of the hydro carbons in oil source and the oil of one or more non-petroleum sourcess comprises one or more and is selected from following oil: rapeseed oil, Viscotrol C, Oleum Cocois, Fructus Coriandri oil, Semen Maydis oil, Oleum Gossypii semen, hazelnut oil, hempseed oil, linseed oil, mango kernel oil, Dow pond caul-fat, sweet oil, plam oil, palm kernel oil, peanut oil, rapeseed oil, Rice pollard oil, Thistle oil, tea plum oil, soybean oil, sunflower seed oil, Yatall MA, Camellia oil and combination thereof.In certain embodiments, base oil is selected from high erucic acid rape seed oil, soybean oil, Thistle oil, rapeseed oil, Viscotrol C, sunflower seed oil and linseed oil.

Charging can comprise the oil of about 1 weight % to the petroleum derivation hydro carbons of about 99 weight % and about 1 weight % to the non-petroleum sources of about 99 weight %.In application, charging comprises and is higher than about 50 weight %, be higher than about 60 weight % or be higher than the petroleum derivation hydro carbons of about 70 weight %.In application, charging comprises and is lower than about 50 weight %, is lower than about 40 weight % or is lower than the petroleum derivation hydro carbons of about 30 weight %.In application, charging comprises ratio and is about 1: 1 the petroleum derivation hydro carbons and the oil of non-petroleum sources.

In embodiments, disclosed system and method is used to hydrofining.In petroleum refining, hydrofining is the process of carrying out in the presence of hydrogen that is used to improve low-viscosity index naphthenic oil and medium viscosity cycloalkanes oil properties.Hydrofining also can be applicable to paraffin, and is used to remove undesired component.Hydrofining consumes hydrogen, and its use is better than acid treatment.As the final step in the base oil factory, hydrofining uses advanced catalysis agent and high pressure (to be higher than 1,000psi) base oil to be carried out final purification.By hydrofining, remaining impurity is transformed into stable base oil molecules (for example UV is stable).Oil by hydrocracking or solvent extraction refining before hydrofining also is used to censure refining, and with the hydrotreatment of straight run lubricating oil distillate become refined lube product both.These lube product comprise naphthenic oil and paraffin oil.Disclosed system and method can be used for the two keys in the saturated hydrocarbonaceous feed logistics.

In embodiments, feed stream comprises for example for example FCC petroleum naphtha or its combination of coking naphtha, catalytic cracking gasoline cut of thermally splitting petroleum fractions.In embodiments, the liquid feeding logistics is included in ebullient naphtha fraction in the gasoline boiling range.In embodiments, the carbon-containing feeding logistics comprises the catalytic cracking gasoline cut.In embodiments, the carbon-containing feeding logistics comprises boiling range at 149 ℃ (300 ℉) the FCC petroleum naphtha to 260 ℃ of (500 ℉) scopes.In embodiments, the carbon-containing feeding logistics comprises the thermally splitting petroleum fractions.In embodiments, the carbon-containing feeding logistics comprises boiling range at 165 ℃ (330 ℉) coking naphtha to 215 ℃ of (420 ℉) scopes.In embodiments, the carbon-containing feeding logistics comprises FCC C6+ petroleum naphtha.

Liquid feeding in the pipeline 13 can comprise various organosulfur compounds, such as but not limited to mercaptan, thiophene, organic sulfide and disulphide etc.Hydrogen-containing gas can be pure basically hydrogen or the gas stream that comprises hydrogen.Without wishing to be bound by theory, hydrogen plays multiple effect, comprise by removing sulfide and produce anion vacancy, the hydrogenolysis [fracture of C-X chemical bond, wherein C is a carbon atom, and X is nitrogen-atoms (hydrodenitrification), Sauerstoffatom (hydrogenation deoxidation) or sulphur atom (hydrogenating desulfurization)] and hydrogenation (net result is the addition of hydrogen).

In embodiments, hydrogen-containing gas is fed directly among the HSD 40, rather than merges with liquid reactants logistics (being the carbon containing fluid) in the pipeline 13.Can operating pumps 5 liquid reactants (liquid feeding for example contains the carbon containing fluid of sulfocompound) pump be crossed pipeline 21, set up pressure and to HSD 40 chargings, so that the controlled flow that spreads all over high-shear device (HSD) 40 and high shear system 1 to be provided.In certain embodiments, pump 5 is increased to the enter the mouth pressure of logistics of HSD above 202.65kPa (2atm), preferably surpasses about 303.975kPa (3atm).In this way, high shear system 1 can be combined with high-shear and pressure, to increase the thorough mixing of reactant.

In embodiments, at first with reactant and if present, catalyzer (for example aqueous solution and catalyzer) mixes in container 10.Reactant enters container 10 through for example source line 14 and 15.It is contemplated that any amount of container entrance pipeline, in Fig. 1, shown two (through pipelines 14 and 15).In embodiments, container 10 is equipped with catalyzer, and if necessary, catalyzer is activated according to the step that catalyzer supply merchant recommends.

After pumping, hydrogen and liquid reactants (liquid feeding, for example carbonaceous liquid that contains sulfocompound in the pipeline 13) mix in HSD 40, and described HSD 40 is used for producing the fine dispersions of hydrogen-containing gas at liquid feeding.In HSD 40, hydrogen-containing gas and liquid feeding are highly dispersed, and have caused forming nano bubble, submicron-scale bubble and/or the microbubble of gaseous reactant, better are dissolved in the solution and increase reactant to mix.For example, the IKA of DR 2000/4 type

Decollator is in bulk the putting of high-shear three fractions of disposing three rotors and stator combination of arranged in series, can be used for producing disperseing the dispersion (i.e. " reactant ") of hydrogen-containing gas in liquid feeding.Rotor/stator sets can for example be configured as shown in Figure 3.The reactant warp 13 that merges enters high-shear device and enters first step rotor/stator sets.The rotor of the first step and stator can have first step rotor tooth and the stator tooth that periphery is separated respectively.The coarse dispersion that leaves from the first step enters second stage rotor/stator.Partial rotor and stator also can comprise rotor tooth and the stator tooth that periphery is separated respectively.The dispersion that the bubble size that comes out from the second stage reduces enters third stage rotor/stator sets, and it can comprise rotor and the stator that has rotor tooth and stator tooth respectively.Dispersion is left high-shear device through pipeline 18.In certain embodiments, shearing rate vertically progressively increases along the direction 260 of stream.

For example, in certain embodiments, the shearing rate of first step rotor/stator is higher than subsequently the shearing rate in the level.In other embodiments, shearing rate is along the direction substantially constant of stream, and the shearing rate in each grade is substantially the same.

If high-shear device 40 comprises the PTFE sealing member, sealing member can use any suitable technology known in the art to cool off.For example, the liquid feeding reactant stream of inflow line 13 can be used for coolant seal spare, and has carried out required preheating thus before entering high-shear device 40.

The speed that the rotor of HSD40 can be configured to match with diameter and required tip speed with rotor is rotated.As above-described, high-shear device (for example colloidal mill or have the decollator of jagged edges) has the fixed interval (FI) between stator and rotor, perhaps have adjustable gap.HSD 40 is used for hydrogen-containing gas and reactant liquid (being the liquid stream that pipeline 13 contains sulfocompound) thorough mixing.In some embodiment of method, reduced the Transport resistance of reactant by the operation high-shear device, it is about more than 5% to make speed of response increase.In some embodiment of method, reduced the Transport resistance of reactant by the operation high-shear device, it is about more than 5 times to make speed of response increase.In certain embodiments, speed of response has increased at least about 10 times.In certain embodiments, speed has increased about 10 times to about 100 times.

In certain embodiments, HSD 40 delivers 300L/h at least with the 4500ft/min at least and the tip speed that can surpass 7900ft/min (40m/s).Watt consumption can be about 1.5kW.Although the real-time temperature and the pressure at the tip of the shearing parts of rotation or spinner member are difficult among the measurement HSD 40, under cavitation conditions, observed local temperature surpasses 500 ℃ in well-mixed reactant according to estimates, and pressure surpasses 500kg/cm ²High shear mixing has caused the bubble dispersion of hydrogen-containing gas with micron or submicron-scale.In certain embodiments, the dispersion that obtains has the average bubble size less than about 1.5 μ m.Therefore, the dispersion of coming out from HSD40 through pipeline 18 comprises the bubble of micron and/or submicron-scale.In certain embodiments, average bubble size at about 0.4 μ m to the scope of about 1.5 μ m.In certain embodiments, the dispersion that obtains has the average bubble size less than about 1 μ m.In certain embodiments, average bubble size is less than about 400nm, and can be about 100nm in some cases.In many embodiments, microbubble dispersion can under atmospheric pressure keep disperseing to last at least 15 minutes.

Can use and be used for the microscopical reverse rotation cone-plate of high-amplification-factor confocal fluorescent formula shear box and study these dispersions under shearing.Microstructure and the dynamic (dynamical) long observation of particle have been obtained to dispersion.Yet for the real space research of 3D system under shearing, main difficulty is that particle passes through the mobile too fast of field of microscope, unless feasible very near the fixed wall that wherein velocity of flow is enough little, otherwise can not follow the trail of it.Although the exploitation of confocal scanning technology may mean major step forward faster, its real answer is to use the reverse rotation shear box.In this method, two parts of box are rotated in the opposite direction, cause forming fixed pan in the inside of box.Can observe the dispersion object that is positioned at this plane for a long time then.

In case after disperseing, the gas/liquid of acquisition or gas/liquid/solid dispersion leave HSD 40 and are fed to container 10 through pipeline 18, as shown in fig. 1.As reactant well-mixed result before entering container 10, the chemical reaction of signal portion may take place in HSD 40 under the situation that has or do not exist catalyzer.Therefore, in certain embodiments, reactor/vessel 10 may be mainly used in heating and separated product hydrogen sulfide from the carbon containing fluid.Alternatively or in addition, container 10 can be used as the principal reaction container, most of hydrogen sulfide product produces therein.For example, in embodiments, container 10 is to comprise catalyst fixed bed fixed-bed reactor.

Vessel/reactor 10 can be with continuous or semicontinuous stream mode operation, and perhaps it can be operated with batch mode.Can use heating and/or cooling way (for example spiral coil cooling tube) and thermometric instruments that the inclusion of container 10 is maintained under the specified temperature of reaction.Can use the pressure in the suitable pressure-measuring instrument monitoring container, and can use the regulator of level (not shown), the reactant liquid level in the known technology control of the professional container in use present technique field.Inclusion can continuous or semicontinuous stirring.

Catalyzer.The catalyzer that uses in various embodiments can be taked the form of fixed bed or slurry.These catalyzer comprise homogeneous catalyst and heterogeneous catalyst the two.

In embodiments, the aluminum oxide base-material that is impregnated with the catalyzer of cobalt and molybdenum is used for the hydrogenating desulfurization of petroleum products.In another embodiment, platinum metals (platinum, palladium, rhodium, ruthenium) catalyst based for example hydrogenation of soybean oil of NDRO oil that is used to.In some cases, the hydrogenation that also non-precious metal catalyzer (for example nickel-base catalyst and copper compound catalyzer) is used for NDRO oil.The example of nickel-base catalyst is Raney nickel (Raney nickel) and lacquer original nickel (Urushibara nickel).

In other embodiments, cobalt (Co) is catalyst based, nickel (Ni) is catalyst based, ruthenium (Ru) is catalyst based, copper (Cu) is catalyst based, palladium (Pd) is catalyst based or platinum (Pt) catalyst based being used for produced amine through the nitrile hydrogenation.What selection of catalysts depended on needs production is primary amine, secondary amine or tertiary amine.

In other embodiments, cobalt (Co) catalyzer, molybdenum (Mo) catalyzer, nickel (Ni) catalyzer, tungsten (W) catalyzer or its combination are used for hydrodenitrification.

If use catalyzer to promote the reduction of S-contained substance, catalyzer can be used as slurry or catalyst stream imports container 10 through pipeline 14 and/or 15.Alternatively or in addition, catalyzer can be added into the elsewhere in the system 1.For example, catalyst pulp can be injected pipeline 21.In certain embodiments, pipeline 21 can contain mobile carbon containing fluid stream, and/or can be connected to pipeline 21 through pipeline 16 from the recirculation stream of for example container 10.

In embodiments, Vessel/reactor 10 comprises the known any catalyzer that is suitable for hydrogenating desulfurization of professional in present technique field.The soluble catalyst that is fit to can be the metallic sulfide of carrying.In embodiments, metallic sulfide is selected from moly-sulfide, cobaltous sulfide, sulfuration ruthenium and combination thereof.In embodiments, catalyst pack Containing Sulfur ruthenium.In embodiments, the binary combination of catalyst pack Containing Sulfur molybdenum and cobaltous sulfide.In embodiments, carrier comprises aluminum oxide.In embodiments, catalyst pack contains the aluminum oxide base-material that is impregnated with cobalt and/or molybdenum.The catalyzer that uses in hydrodesulfurisationstep step can be the conventional desulfurization catalyst that is made of on the refractory support that is fit to VI family and/or VIII family metal.In embodiments, hydrotreating catalyst comprises refractory support, and it is selected from silicon-dioxide, aluminum oxide, silica-alumina, silicon-dioxide-zirconium white, silica-titania, titanium oxide and zirconium white.VI family metal can be molybdenum or tungsten, and VIII family metal is generally nickel or cobalt.Hydrobon catalyst can comprise the high surface area gamma-aluminium oxide carrier that is impregnated with blended sulfide, is typically CoMo or NiMo.In embodiments, Hydrobon catalyst comprises MoS2 and more a spot of other metals, and it is selected from molybdenum, cobalt, nickel, iron and combination thereof.In embodiments, catalyzer comprises zinc oxide.In embodiments, catalyzer comprises molybdenum and nickel and/or the cobalt hydrotreating catalyst that conventional prevulcanized thing is handled.

In embodiments, catalyzer is taked the aluminosilicate form.In embodiments, catalyzer is the zeolite of intermediate pore size, for example has the zeolite of ZSM-5 topological framework.Although owing to have hydrogen and sulphur in the reaction zone, catalyzer may experience chemical transformation in reaction zone, when catalyzer at first contacted with the carbon-containing feeding logistics, it can take the form of oxide compound or sulfide.When system and method during at hydrodenitrification, the catalyzer of molybdenum on aluminum oxide that can select cobalt to help to urge is used for hydrogenating desulfurization.For hydrodenitrification, it may be the ideal catalyzer that nickel helps the catalyzer of molybdenum on aluminum oxide of urging.

Catalyzer can pass through at high temperature to contact with for example hydrogen, or regenerates by burning in air or other oxygen-containing gass.

In embodiments, container 10 comprises the fixed bed that is fit to catalyzer.In certain embodiments, add catalyzer through pipeline 15 continuously to container 10.In embodiments, the use of external pressurized high-shear device reactor provides the hydrogenating desulfurization that does not need catalyzer, as what further discuss in the following Example 1.

Ideally, the main body of reactant or integrated operation temperature maintenance are being lower than its flash-point.In certain embodiments, the operational condition of system 1 comprises about 100 ℃ of temperature to about 230 ℃ of scopes.In embodiments, temperature is in about 160 ℃ to 180 ℃ scope.In specific embodiments, the temperature of reaction in the container 10 specifically about 155 ℃ to about 160 ℃ scope.In certain embodiments, the reaction pressure in the container 10 at about 202.65kPa (2atm) to the scope of about 5.6Mpa-6.1MPa (55-60atm).In certain embodiments, reaction pressure at about 810.6kPa to the scope of about 1.5MPa (8atm extremely about 15atm).In embodiments, container 10 is operated under normal atmosphere or nearly normal atmosphere.For example be used for petroleum naphtha hydrogenation purified embodiment, the pressure of container 10 can for about 345kPa (50psi) to about 10.3MPa (1500psi), and temperature of reaction is at about 260 ℃ (500 ℉) extremely in the scope of about 427 ℃ (800 ℉).For example be used for petroleum naphtha hydrogenation purified embodiment, the pressure of container 10 can for about 2.0MPa (300psi) to the scope of about 6.9MPa (1000psi), and temperature of reaction is at about 371 ℃ (700 ℉) extremely in the scope of about 427 ℃ (800 ℉).

Randomly, if desired, dispersion can further be processed before entering container 10.In container 10, by carrying out/continue hydrogenating desulfurization with hydrogen reducing.Can carry out continuous or semicontinuous stirring to the inclusion of container, can control the temperature of (for example using heat exchanger) reactant, and can use the fluid level of standard technique regulation and control container 10 inside.According to the needs of concrete application, hydrogen sulfide can be with continuous, semicontinuous or produce by batch mode.The product hydrogen sulfide that produces can leave container 10 through gas tube 17.This gas stream can comprise for example unreacted hydrogen and product hydrogen sulfide.In embodiments, reactant is selected, be lower than about 6% unreacting hydrogen by weight so that gas stream comprises.In certain embodiments, the reacting gas stream in the pipeline 17 comprises about by weight 1% to about 4% hydrogen.Can further handle the reactant gases that removes through pipeline 17, and if desired, can be with the component recycle.

Reaction product stream is left container 10 by pipeline 16.In embodiments, the product logistics in the pipeline 16 comprises the dissolved hydrogen sulfide, and as hereinafter further handling therefrom to remove hydrogen sulfide of discussing.In other embodiments, imagination product hydrogen sulfide leaves container 10 through pipeline 17, and comprises the carbon containing fluidic product liquid that therefrom removes sulfocompound, leaves container 10 through pipeline 16.

In some optional application of embodiment, the integral part (for example nitrogen) from the hydrofining of petroleum naphtha is carried out hydrotreatment with the preparation amine.Amine is hexanediamine, propylamine, butylamine, benzene methanamine, tallow amine, ethamine etc. for example, can be by organic nitrile for example propionitrile, butyronitrile, tallow nitrile, acetonitrile etc., catalyzer and other materials for example ammonia and/or caustic alkali in the presence of carry out shortening and produce.

The nitrile hydrogenation with produce amine industrial be very important, this is because the widespread use of amine, for example as organic solvent, agrochemicals, medicine, tensio-active agent and particularly nylon-6,6 intermediate.

Ding Yi organic nitrile contains at least one nitrile herein, be also referred to as cyanogen (--CN) base.Organic materials can be the nitrile of aliphatic series, aromatic series, cyclic aliphatic, heterocycle family, family of heterolipid family, for example alkylene oxide and amine and cyano ethyl product etc. thereof.Organic materials also can have above nitrile group, amido and a nitrile group, and also can be undersaturated.Dimer fatty dintrile and unsaturated fatty acids dimer dintrile are preferred parent materials, but also can use other nitriles, comprising: vinyl cyanide, methacrylonitrile, propionitrile, cyanobenzene, the 2-methyl cellosolve acetate glutaronitrile, isopropyl cyanide, dicyano cyclooctane, itrile group three acetonitriles, m-dicyanobenzene and terephthalonitrile, 1,3,5-tricyano benzene, neighbour, between or to the methylbenzene nitrile, adjacent, between or the p-aminophenyl formonitrile HCN, phthalonitrile, phenyl trimethylsilyl nitrile, the 1-naphthyl cyanide, 2-naphthyl cyanide, cyclobutyronitrile, the ring valeronitrile, cyclohexanenitrile, 1,4-hexamethylene dintrile, 1,2,4,5-hexamethylene four nitriles, ring heptonitrile, 3-methyl ring heptonitrile, ring caprylic nitrile, butyronitrile, valeronitrile, own nitrile, 2,2-dimethyl propionitrile, heptonitrile, caprylic nitrile, pelargonitrile, n-capric nitrile, undecanonitrile, lauronitrile, dodecyl cyanide, tridecyl cyanide, pentadecane nitrile, palmitonitrile, the heptadecane nitrile, stearonitrile, phenylacetonitrile, propane dinitrile, succinonitrile, trimethylene cyanide, adiponitrile, 1,3,5-tricyano pentane, 4-methyl-3-hexene dintrile, 4-ethyl-3-hexene dintrile, 5-methyl-4-nonene dintrile, 5-ethyl-4-decene dintrile, 7-methyl-6-tridecylene dintrile, 7-methyl-6-ten pentaene dintrile, 12-methyl isophthalic acid 2-two tetradecene dintrile, 10-hexyl-9-two tetradecene dintrile, 2,3-dimethyl-3-hexene dintrile, 2,4,6-trimethylammonium-3-heptene dintrile, 4-ethyl-6,7-dimethyl-3-octene dintrile, 2,4,6-triethyl-3-octene dintrile, 2-ethyl-4,6-dipropyl-3-octene dintrile, 2-methyl-4,6,8,10-tetrapropyl-3-laurylene dintrile, 2,4,7,9,11,13,15-seven ethyls-6-hexadecylene dintrile, 3-methylene radical adiponitrile, 4-methylene radical pimelonitrile, 5-methylene radical azelaic dinitrile, 6-methylene radical undecane dintrile, 7-methylene radical tridecane dintrile, 8-methylene radical pentadecane dintrile, 12-methylene radical tetracosane dintrile, 15-methylene radical nonacosane dintrile, 2-methyl-3-methylene glutaronitrile, 2,4-dimethyl-3-methylene glutaronitrile, 2-methyl-4-methylene radical suberonitrile, 2-methyl-7-ethyl-4-methylene radical suberonitrile, 2,4,8-trimethylammonium-6-methylene radical dodecane dintrile, 2,4,8,10-tetrapropyl-6-methylene radical dodecane dintrile, 2,26-dimethyl-14-methylene radical heptacosane dintrile, aminoacetonitriles, hexanaphthene-1,6-dintrile, methyl alcohol, ethanol, butanols, the derivative of the cyano ethylization of amylalcohol etc.; From methylamine, ethamine, butylamine, octylame, ethylene glycol, propylene glycol, butyleneglycol, propylene glycol, Diethylene Glycol, dipropylene glycol, Resorcinol, Phloroglucinol, 1, the 4-cyclohexanediol, 1,4-two (methylol) hexanaphthene, polyoxyethylene glycol, polypropylene glycol, the polyoxyalkylene polyethers, polyester polyol, from oxyethane and/or propylene oxide and methylene dianiline (MDA) and poly-ethylidene polyaniline mixture deutero-polyvalent alcohol affixture, vinyl enhanced polyether glycol, for example pass through the polyvalent alcohol that vinylbenzene or the vinyl cyanide polyreaction in the presence of polyethers obtains, from the glycol polyacetal of Diethylene Glycol and formaldehyde for example, polycarbonate polyol is for example from butyleneglycol and diaryl carbonate, the resole polyvalent alcohol, the hydroxyl terminated poly-butadiene resin, quadrol, butanediamine, polyamine is primary amine terminated polyether resin etc. for example, and composition thereof.

Wherein nitrogen is called as aromatic amine with the amine that aromatic nucleus directly links to each other, and is mass-produced important intermediate.The hydrogenation of nitroaromatic is a strong exothermal reaction.Therefore, reaction dissipation of heat and energy utilization are the important factors during nitroaromatic is produced.Make the initial aromatic nitro compound of aromatic amine is represented by following general formula as raw material:

Wherein R represents adjustable length hydrocarbon chain.

Many commercialization reactions of producing amine involve the gas phase hydrogenation of nitroaromatic.Fluidized-bed reactor is assisted dissipation of heat, but has the shortcoming of inconsistent and catalyst attrition of residence time in reactor.

The additive method that is used for producing amine has utilized the stagnant catalyst of fixed bed.Fixed-bed reactor have control preferably to the residence time, and have also avoided the catalyst attrition problem.The adiabatic usually operation of these fixed-bed reactor is with the controlled temperature that circulates by a large amount of gases.

The hydrogenation of organic nitrile is also carrying out in the presence of Raney nickel catalyst under high temperature and the hydrogen pressure in liquid phase, wherein has ammonia so that increase the yield of primary amine by the formation that suppresses secondary amine and tertiary amine.Also can use sponge nickel or cobalt water paste catalyzer or precious metal catalyst in Ruan.Catalyzer can use under the situation that does not have or have promotor.Promotor is for example Fe, Mo, Cr, Ti, Zr.Catalyzer can be applied on the solid support material.Such solid support material is SiO for example ₂, Al ₂O ₃, ZrO ₂, MgO, MnO, ZnO, Cr ₂O ₃

The existing method that is used to produce amine also has the shortcoming of discharging and particularly disposing decaying catalyst, and this causes catalyst loss.

In the embodiment of the present disclosure that in as Fig. 5, shows, enter before the fixed bed catalyst bed that contains hydrogenation catalyst at hydrogen, use high-shear mixer hydrogen to be dispersed in advance the bubble of submicron and micron-scale in organic nitrile compounds (containing or do not contain other organic thinner).

Adopt the hydrogen of submicron and micron-scale bubble form, when being exposed to catalyzer, allow more effective and heterogeneous reaction to take place with organic nitrile.Again circulate by high-shear mixer, also help to have promoted hydrogenation reaction.

Controlling flow is crossed the stream and the reactor pressure of system, can control by the positive-displacement pump of high-shear mixer ingress.Because reaction is heat release, can control fluid temperature (F.T.) by using the heat exchanger that links to each other with the hydrogen-catalyst reactor discharge.Also can control heat accumulation by the flow velocity that flows through reactor.Also can add inert diluent to help temperature control to reactant.

Compare with the amine means of production of routine, the system that obtains needs less laid down cost, and reaction conditions is had better control.Fixed-bed reactor also avoided to the needs of isolating catalyzer and with fluidized-bed or the relevant catalyst attrition of slurry reaction process.

Repeatedly transfer operation.In Fig. 1 embodiments shown, system is configured for single pass operation, wherein directly further processes from the output 16 of container 10, to reclaim sulphur and carbon containing fluid.In certain embodiments, may need the inclusion of container 10 or contain liquid fraction part of unreacted sulfocompound, in transmission second time process by HSD 40.In this case, pipeline 16 can link to each other with pipeline 21 as dotted line pipeline 20 is indicated, makes at least a portion inclusion of pipeline 16 circulate again from container 10, and is pumped into pipeline 13 and therefore entered HSD 40 by pump 5.Additional hydrogen-containing gas can inject pipeline 13 through pipeline 22, and perhaps it can directly add (not shown) in the high-shear device to.In other embodiments, before sweetening liq is not re-circulated to high-shear device 40 with the part in the product logistics, can further handle (for example from wherein removing hydrogen sulfide) to the product logistics in the pipeline 16.

A plurality of high shear device.In certain embodiments, two or more similar HSD40 or construct different high-shear device arranged in series are used for further intensified response.Their operation can be taked partial or continuous mode.Need under the situation of single transmission or " once passing through " method at some, it also may be favourable using placed in-line a plurality of high-shear device.In the embodiment of some a plurality of high-shear device serial operation, can omit container 10.For example, in embodiments, the outlet dispersion in the pipeline 18 can be fed to second high-shear device.When a plurality of high-shear device 40 serial operations, additional hydrogen can be injected in the inlet feed stream of each device.In certain embodiments, a plurality of high-shear device 40 parallel operations are imported in one or more containers 10 from their outlet dispersion.

Downstream processing.Fig. 2 is another embodiment of high shear system 300, wherein aforesaid high-shear device 40 is incorporated into for example in the conventional industrial hydrodesulfurization unit seen in the refinery.HDS system 300 comprises fresh feed pump 5, comprises the liquor pump source line 21 for the treatment of hydrogenating desulfurization liquid and is pumped into external high shear device 40 by fresh feed pump 5, to improve hydrodesulfurization process.By the disclosure,, use high-shear device 40 that hydrogen-containing gas 22 and sulfocompound seen in the petroleum products that carries out hydrogenating desulfurization are usually merged and react as above-mentioned.The pressure of the liquid phase feed stream in the pipeline 21 increases through pump 5.Just as noted before, pump 5 can be positive-displacement pump or toothed gear pump.Pump discharge logistics in the pipeline 13 mixes with dispersible hydrogeneous reactant stream through pipeline 22, and is imported into the inlet (for example 205 among Fig. 3) of external high shear device 40 through high-shear device source line 13.Positive-displacement pump (or toothed gear pump) 5 chargings also are metered into the gas-liquid mixture that external high shear device 40 enters the mouth.As discussed above, the mixing in the external high shear device 40 have produced the dispersion that comprises hydrogen microvesicle (and/or submicron-scale bubble), and have promoted to be used for the reaction conditions that the sulphur compound of hydrogen and organic charging reacts.Therefore, the micron and/or the submicron-scale bubbles dispersion body of discussion during the outlet of the high-shear device in the pipeline 18 logistics comprises as mentioned.As usual, liquid feeding is reached high pressure through pipeline 21 by pump, and in the pipeline 22 that comprises rich hydrogen recycle gas, converge with gas, the mixture that obtains is preheated (may change heating by caloric value through heat exchanger), then pre-warmed feed stream is sent to the fired heater (not shown), incoming mixture was vaporized in this fired heater before entering container 10 and is heated to high temperature.As a comparison, in high-shear hydrogenating desulfurization system 300, the dispersion from high-shear device 40 in the pipeline 18 comprises the dispersion of hydrogeneous bubble in the liquid phase that comprises carbonaceous liquid and sulfocompound.In fixed-bed reactor 10, when the reactor inlet dispersion in the pipeline 18 flows through the fixed bed of catalyzer, hydrogenating desulfurization takes place.In embodiments, reactor 10 comprises trickle-bed reactor.In embodiments, under the temperature and the high pressure of absolute pressure in 101.325kPa-13.2MPa (1 to 130 normal atmosphere) scope of the hydrodesulfurization reaction in the reactor 10 in 100 ℃ to 400 ℃ scopes, in the presence of catalyzer, take place.

Thermal response product in the pipeline 16 can carry out the part cooling by flowing through heat exchanger 80, and described heat exchanger also can be used for preheating is carried out in the reactor feed in the pipeline 21.The reactor product logistics of heat exchange in the pipeline 42 flows through water-cooled heat exchanger then, experiences pressure then and reduces (being shown as pressure controller PC, 50), is reduced to about 303.9kPa-506.6kPa (3 to 5 normal atmosphere).The liquid that obtains in the pipeline 43 and the mixture of gas enter gas separator container 60 under the absolute pressure of for example about 35 ℃ and 303.9kPa-506.6kPa (3 to 5 normal atmosphere).

Sent amine contactor 30 with the hydrogen-rich gas from gas separator container 60 in the pipeline 44, to remove the reaction product H that it is comprised ₂S.Also can from product gas, remove and reclaim ammonia, be used for for example fertilizer application.Part in the pipeline 54 there is not H ₂The S hydrogen-rich gas circulates back again, use in high-shear device 40 and reactor 10 again, and pipeline 53 can not have H with a part ₂The S hydrogen-rich gas is by pipeline 54 guiding other places (for example purging).As hereinafter further discussing, can from pipeline 44, isolate a part in the pipeline 44 from the gas that is rich in hydrogen sulfide of gas separator container 60 by pipeline 45.The hydrogen sulfide that removes and reclaim by the amine gas treatment unit 30 in the amine logistics that is rich in hydrogen sulfide in the pipeline 48 further can be transformed into elementary sulfur (for example in Crouse (Claus) square law device).Can use Crouse's method with the hydrogen sulfide oxidation, to produce water and to reclaim elementary sulfur.

Liquid stream from gas separator container 60 in the pipeline 49 can be sent to downstream processing.For example, in Fig. 2, downstream processing comprises the stripping distillation tower 70 that boils again, comprises thus in the bottoms of sweetening liq product sulfurous gas is removed in the gas tube 51 from pipeline 52.The sulfurous gas that autoreaction product liquid stripping obtains in the pipeline 51 can be chosen the sulfurous gas in pipeline 45 wantonly, is sent to central treatment plant.May comprise hydrogen, methane, ethane, hydrogen sulfide, propane and possible butane and heavier hydro carbons from the cat head sulfurous gas of stripping desorption tower 70 in the pipeline 51.The processing of this gas (not showing in Fig. 2) can be reclaimed propane, butane and pentane or heavier component.Remaining hydrogen, methane, ethane and some propane can be used as the refinery fuel gas body.If the liquid feeding in the pipeline 21 comprises alkene, the cat head sulfurous gas in the pipeline 51 also may comprise ethane, propylene, butylene and amylene or heavier component.Can derive by the main amine gas treatment unit (showing among Fig. 2) from refinery through 47 amine aqueous solutions that import resorbers 30 that enter the mouth, and the amine that is rich in hydrogen sulfide in the resorber outlet line 48 can turn back to the main amine gas treatment unit (showing among Fig. 2) of refinery.

The product liquid of the hydrotreatment/hydrofining in the pipeline 52 can be sent to for example catforming process, to increase octane value (it may reduce through after hydrotreatment/hydrofining).The catalytic reforming of the desulfurization product in the pipeline 52 will produce hydrogen, and it can be re-circulated to HDS 40 in embodiments.

The surface-area of the increase of the micron-scale in dispersion that produces in high-shear device 40 in the pipeline 18 and/or the bubble hydrogen of submicron-scale causes reacting faster and/or more completely of hydrogen and the sulphur compound in the feed stream that pipeline 21 imports.As what above mention, other benefits are the abilities of operating under lesser temps and pressure, have caused the saving of operation and capital construction cost.Hydrotreater/hydrofinisher 10 operation at a lower temperature can minimize so that the undesired octane of carbon-containing feeding logistics reduces.The benefit of system and method for the present disclosure, include but not limited to the flux of cycling time, increase faster, and owing to can design littler reactor and/or operation reactor and may cancel the running cost of the reduction that catalyzer causes and/or the capital cost of reduction under lesser temps and/or pressure.

In embodiments, high-shear hydrogenating desulfurization system and method for the present disclosure is suitable for total sulfur content is reduced to the scope that is lower than millions of/one, thereby prevented/alleviated the poisoning of precious metal catalyst in the catalytic reforming step subsequently (for example the catalytic reforming of petroleum naphtha) subsequently.In embodiments, charging comprises diesel oil, and the HDS system and method is used to reduce the sulphur content of fuel, makes it satisfy the requirement of ultra-low-sulphur diesel (ULSD).In embodiments, the sulphur content of fuel is lower than about 300ppm by weight.In embodiments, be lower than about 30ppm by weight.In other embodiments, be lower than about 15ppm by weight.

Also can use hydrogenolysis to reduce the nitrogen content (hydrodenitrification or HDN) of charging.In embodiments, the system and method that is used for the hydrogenating desulfurization of feed stream also is used for simultaneously to a certain extent to the logistics denitrogenation.Disclosed system and method also can be used for saturated (hydrogenation) hydro carbons, for example is used for alkene is transformed into alkane.In embodiments, disclosed system and method can be used for the saturated of alkene separately, perhaps can be used for desulfurization simultaneously, denitrogenation and/or alkene is saturated to corresponding alkane.Disclosed system and method can be used as hydrofinishing process (for example comprising the hydrofining of the logistics of petroleum naphtha), with the physicochemical property of the oils of removing non-hydrocarbons integral part (for example sulphur, nitrogen etc.) and/or improve producing, for example color, viscosity index, inhibition are replied, oxidation and thermostability.In some application of embodiment, the integral part that is removed can be used in the high-shear mixer, and is used for the amine of various commercial applications with production by hydrogenation.

By the mixing of HSD 40 increase reactants, this application allows potentially to carbonaceous stream hydrogenating desulfurization better.In certain embodiments, the enhanced mixing makes the increase of handled thing circulation become possibility.In certain embodiments, high shear device is incorporated in the processing method of having set up, thereby can increases production (promptly higher flux).Attempt with some that to increase the hydrogenating desulfurization degree methods opposite by increasing temperature of reactor simply, by superior dispersion that external high shear provided with contact, can allow to reduce overall operation pressure in many cases, keep simultaneously or even increase speed of response.Do not wish to be subjected to concrete theoretical restriction, it is believed that the level of high shear mixing or degree are enough to increase quality transfering rate, and produce local non-ideal condition, this can make originally and according to Gibbs free energy prediction expectation impossible reaction be taken place.Local non-ideal condition it is believed that in that high-shear device is inner and takes place, and causes the temperature and pressure that increases, and wherein the most significant increase it is believed that it is the increase of local pressure.The increase of pressure and temperature is instant with partial in the high-shear device, in case after leaving high-shear device, with regard to rapid return to main body or average system condition.In some cases, high shear device is induced the cavatition of sufficient intensity, and one or more reactants are dissociated into free radical, and it can aggravate chemical reaction, or allows to be reflected to compare under the lower condition of harsh property with the condition of common needs and take place.Cavatition also can be by producing the speed that local turbulence and liquid microcirculation (acoustics flows) increase transportation.Handle the general introduction of using cavitation phenomenon in the application in chemical/physical, be provided at (Cavitation:A technology on the horizon) in " cavatition: emerging technology ", Current Science 91 (No.1): 35-46 (2006) by Gogate etc.).The high shear device of some embodiment of system and method for the present invention is induced cavatition, thus hydrogen and sulfocompound is dissociated into free radical, and they react then, produces the product that comprises hydrogen sulfide.

In certain embodiments, system and method described herein with comparing of may accomplishing under the situation of not using in the past external high shear device 40, allows the technology that design is littler and/or capital-intensity is lower.The potential advantage of some embodiment of method of the present disclosure is to reduce the running cost of existing processing method and increase its output.Some embodiment of processing method of the present disclosure also provides the advantage of the fund cost that reduces the design novel process.In embodiments, use high-shear device 40 that hydrogen-containing gas is dispersed in the carbon containing fluid that comprises sulfocompound, reduced the amount of unreacted sulfocompound.The potential benefit of some embodiment that this is used for the system and method for hydrogenating desulfurization includes but not limited to the flux of cycling time, increase faster, higher conversion and owing to designing littler reactor and/or the running cost of the reduction that operation causes under lesser temps and/or pressure and/or the capital cost of reduction.

In embodiments, carry out the use of reactant blended method disclosed comprising by external high shear device 40, allow in Vessel/reactor 10, to use than before the lower temperature and/or the pressure that are allowed.In embodiments, method comprises external high shear device 40 is incorporated in the processing method of having set up, reduce operation temperature and/or pressure in the external high shear device 40 thus, and/or can be increased in the production (higher flux) of the technology of operating under the condition of not using high-shear device 40.In embodiments, container 10 is mainly used in the fluidic cooling, because most of reaction occurs in the external high shear device 40.In embodiments, container 10 is being operated near under the normal atmosphere.In embodiments, the great majority reaction occurs in external high shear device 40 inside.In embodiments, hydrogenating desulfurization mainly occurs in the high-shear device that does not use catalyzer.

Disclosed by using hydrogen to carry out the method and system of liquid-phase reduction with the hydrogenating desulfurization of carbon containing fluid, used outside high shear mechanical device that quick contact and mixing under the controlled environment of chemical ingredients in reactor/high-shear device are provided.Thereby high-shear device has reduced the mass transfer limitations of reaction and has increased overall reaction rates, and can allow sulphur and hydrogen may not can to take place in expectation under the overall operation condition of substantive reaction substantive the reaction to be taken place.

Although shown and described the preferred embodiments of the invention, the professional in present technique field can make amendment and not deviate from spirit of the present invention and instruction it.Embodiment described herein only is exemplary, is not intended to limit.The many variations and the modification of invention disclosed herein are possible, and are within the scope of the present invention.When numerical range or limit by clear and definite narrative tense, the scope of these statements or limit should be understood that to have comprised the eclipsed scope of the scope that is in clearly statement or the same value in the limit or limit (for example from about 1 to about 10 has comprised 2,3,4 etc.; Comprised 0.11,0.12,0.13 etc. greater than 0.10).For the key element of any claim, use term " alternatively ", purpose is meant that target component needs, or unwanted.Two kinds of selection schemes all plan to be included within the scope of claim.For example comprise (comprises), comprise (includes), have the use of (having) etc. than the generalized term, should be understood that into than the term of narrow sense for example by ... form (consisting of), basically by ... form (consisting essentially of), basically by ... formation (comprised substantially of) etc. provides support.

Therefore, the scope of protection is not subjected to the restriction of the description that proposes above, but only is subject to following claims, and its scope comprises all equivalent way of the subject content of claims.Each and all claims are incorporated in the specification sheets as embodiment of the present invention.Therefore, claims are further descriptions, are replenishing of the preferred embodiments of the invention.The disclosure of the patent that all this paper quote, patent application and publication provides in the content that they propose for this paper on the degree of replenishing of exemplary, procedural or other details, draws at this to be reference.

Claims (20)

1. be used for the method for hydrogenating desulfurization, hydrodenitrification, hydrofining, amine production or its combination, described method comprises:

Formation contains the dispersion that is dispersed in the hydrogeneous bubble in the liquid feeding, and wherein bubble has the mean diameter less than about 5 μ m, and wherein charging comprises the mixture of the renewable oils of petroleum derivation hydro carbons and natural origin.

2. the process of claim 1 wherein that charging comprises the hydro carbons that is selected from natural gas liquids, crude oil, crude oil fractions, gasoline, diesel oil, petroleum naphtha, kerosene, rocket engine fuel, oil fuel and combination thereof.

3. the process of claim 1 wherein form dispersion comprise the mixture that makes hydrogen-containing gas and liquid feeding stand to be higher than about 20,000s ^-1Shearing rate.

4. the method for claim 1, wherein forming dispersion comprises hydrogen-containing gas is contacted in high-shear device with liquid feeding, wherein high-shear device comprises at least one rotor, and wherein during dispersion forms at least one rotor with 22.9m/s at least (4, tip speed rotation 500ft/min).

5. the method for claim 4, wherein high-shear device produce at the tip of at least one rotor at least about 1034.2MPa (150, local pressure 000psi).

6. the method for claim 4, wherein the energy expenditure of high-shear device is higher than 1000W/m ³

7. the method for claim 1, it comprises also dispersion is contacted with catalyzer that described catalyzer has activity to hydrogenating desulfurization, hydrodenitrification, hydrofining, amine production or its combination.

8. the method for claim 7, wherein catalyzer comprises homogeneous catalyst and heterogeneous catalyst.

9. the method for claim 7, wherein catalyzer is used for fixing that bed is used or during slurry uses.

10. the method for claim 7, wherein catalyzer comprises the metal that is selected from cobalt, molybdenum, ruthenium, platinum, palladium, rhodium, nickel, copper, tungsten and combination thereof.

11. be used for the method that hydrogenating desulfurization, hydrodenitrification, hydrofining or amine are produced, described method comprises:

Make the fluid mixture that comprises hydrogen-containing gas and liquid feeding in high-shear device, stand to be higher than 20,000s ^-1Shearing rate to produce the dispersion of hydrogen in liquid feeding external phase, wherein liquid feeding comprises the mixture of the renewable oils of petroleum derivation hydro carbons and natural origin; And

Dispersion is imported in the fixed-bed reactor, remove reactor product from described fixed-bed reactor, wherein fixed-bed reactor comprise the catalyzer that is effective to hydrogenating desulfurization, hydrodenitrification, hydrofining, amine production or its combination.

12. the method for claim 11, it also comprises:

Reactor product is separated into gas stream and the liquid product stream that comprises the sweetening liq product;

From gas stream, remove hydrogen sulfide, produce poor hydrogen sulfide logistics; And

The poor hydrogen sulfide logistics of at least a portion is re-circulated to high-shear device.

13. the method for claim 12, it also comprises reforms to the sweetening liq product.

14. the method for claim 12, it also comprises from the product liquid recovery hydrogen of reforming, and is circulated to the hydrogen that a few part reclaims again.

15. the method for claim 11, wherein catalyzer comprises the metal that is selected from cobalt, molybdenum, ruthenium, platinum, palladium, rhodium, nickel, copper, tungsten and combination thereof.

16. a method, it comprises:

Hydrogen is dispersed in high-shear device in the fluid mixture that comprises liquid feeding to produce the dispersion of hydrogen in liquid feeding external phase, wherein liquid feeding comprises the mixture of the renewable oils of petroleum derivation hydro carbons and natural origin; And

Import the catalyst pulp that comprises catalyzer in dispersion, described catalyzer for hydrogenating desulfurization, hydrodenitrification, hydrofining, amine production or its combination effectively.

17. the method for claim 16, wherein catalyzer comprises the metal that is selected from platinum, palladium, rhodium, ruthenium and combination thereof.

18. the method for claim 16, wherein catalyzer comprises the metal that is selected from nickel, copper and combination thereof.

19. the method for claim 16, wherein catalyzer comprises the metal that is selected from cobalt, nickel, ruthenium, copper, palladium, platinum and combination thereof.

20. the method for claim 16, wherein catalyzer comprises the metal that is selected from cobalt, molybdenum, nickel, tungsten and combination thereof.

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