CN104560143A - Two-segment-charged alkylation reaction method - Google Patents

Two-segment-charged alkylation reaction method Download PDF

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Publication number
CN104560143A
CN104560143A CN201310503477.7A CN201310503477A CN104560143A CN 104560143 A CN104560143 A CN 104560143A CN 201310503477 A CN201310503477 A CN 201310503477A CN 104560143 A CN104560143 A CN 104560143A
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reactor
bed
circulating cooling
alkylation
cooling gas
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CN104560143B (en
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彭德强
王璐瑶
孟凡飞
陈建兵
王岩
王阳峰
孟凡忠
陈新
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G50/00—Production of liquid hydrocarbon mixtures from lower carbon number hydrocarbons, e.g. by oligomerisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2/00—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms
    • C07C2/54—Preparation of hydrocarbons from hydrocarbons containing a smaller number of carbon atoms by addition of unsaturated hydrocarbons to saturated hydrocarbons or to hydrocarbons containing a six-membered aromatic ring with no unsaturation outside the aromatic ring
    • C07C2/56—Addition to acyclic hydrocarbons
    • C07C2/58—Catalytic processes
    • C07C2/62—Catalytic processes with acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1081—Alkanes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1088—Olefins
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • General Chemical & Material Sciences (AREA)

Abstract

The invention discloses a two-segment-charged alkylation reaction method. The alkylation reaction method comprises the steps: enabling concentrated sulfuric acid and isobutane to enter a colloid mill, and thoroughly mixing, so as to form an emulsion; enabling the emulsion and a hydrocarbon mixture containing C3-C5 alkene and isobutane to enter an alkylation reactor for reaction, wherein the reactor comprises a tube body, closure heads, an inner revolving bed, an outer revolving bed, a charging pipe, a charge distribution pipe, a discharging opening, a circulating cooling gas inlet and a circulating cooling gas outlet; the inner revolving bed is connected with an upper driving device through the charging pipe, the upper end of the inner revolving bed and the charge distribution pipe are fixedly connected into an integrated structure through a sealing member, the upper part of the outer revolving bed and a reactor shell body are fixedly connected through a sealing member, and the outer revolving bed is connected with a lower driving device through a revolving shaft. The alkylation reaction method disclosed by the invention has the advantages that the degree of mixing of isobutane and concentrated sulfuric acid can be greatly increased, the reaction can be carried out at relatively low temperature, the acid consumption of the reaction is low, the quality of products is high, and the equipment scale is small.

Description

A kind of two section feeding alkylation reaction technique methods
Technical field
The present invention relates to a kind of alkylation reaction method, specifically a kind of alkylation reaction method adopting Trimethylmethane and C3 ~ C5 olefin catalytic alkylated reaction.
Background technology
Along with Economic development, the particularly fast development of transportation, the discharge of Vehicular exhaust is one of air-polluting main source, and improving quality of gasoline is the main approach reducing Vehicular exhaust pollution.The alkylate oil that the alkylated reaction of Trimethylmethane and C3 ~ C5 alkene obtains, having, research octane number (RON) high without sulphur, high-octane rating and the feature such as motor-method octane number difference is little, is the important blend component of high quality clean gasoline.
Alkylated reaction is the conventional art in refining of petroleum field, mainly contains sulfuric acid process alkylation techniques and hydrogen fluoride alkylation techniques, and under the effect of catalyzer (sulfuric acid or hydrofluoric acid), isobutane and olefins is obtained by reacting isoparaffin.Sulfuric acid process alkylation is compared with hydrogen fluoride alkylation, and technique differs from one another, and also all very close from aspects such as initial cost, production cost, product yield and quality producies, therefore this two kinds of method energy long-term co-existence, is all widely adopted.On the whole, from the quantity of alkyl plant and the output of alkyl oil, current hydrofluoric acid alkylation unit is dominant, but in recent years along with the increasingly stringent of environmental regulation requirement and the hypertoxic characteristic of hydrofluoric acid, new device many employings alkyl sodium sulfate metallization processes.
In sulfuric acid process alkylation techniques, reaction is carried out at relatively low temperature, and reaction unit needs to have refrigerating function.In hydrogen fluoride alkylation techniques, temperature of reaction is relatively high, and namely the general water-cooled that adopts can meet reaction requirement.Therefore, both reactor assembly differences are larger.Traditional sulfuric acid process alkylation reactor structure species is more, and what use was more at present has two kinds, and one is cascade sulfuric acid alkylation reaction unit, and one is Stratco formula reactor (i.e. the inner indirect refrigeration reactor arranging heat-obtaining tube bank).
The reactor of cascade sulfuric acid alkylation device is generally made up of several conversion zones, separate with over-pass between each conversion zone, each conversion zone is equipped with agitator, and reaction product and sulfuric acid finally enter settling section and is separated, and the sulfuric acid recycle pump separated is sent into conversion zone and reused.Adopt reactant Trimethylmethane self-evaporatint n. refrigeration, the advantage of this reactive system be alkane alkene in each conversion zone than high, power consumption is little, do not need another refrigerant feeding.But because alkane and alkene are not pre-mixed, thus reduce alkylate oil quality, add sour consumption.And influence each other between each conversion zone, a conversion zone operation is abnormal, and whole reactor is all affected.
A kind of concrete structure of indirect refrigeration reactor that inside arranges heat-obtaining tube bank is that to adopt be horizontal eccentric reactor, the shell of reactor is a horizontal pressurized vessel, a powerful agitator is equipped with in inside, internal recycle sleeve and heat-obtaining tube bank, hydrocarbon raw material enters reactor by upper and lower two feed-pipes, reactor is sprayed into towards impeller after converging before paddle wheel, the impeller run up is in reactor undergauge place, make the logistics of inside reactor due to impeller suction, tuze bundle resistance force, linear differential etc. and cause the hole of some flow liquids, thus make sulfuric acid and hydro carbons obtain reasonable dispersion and mix.Acid hydrocarbon emulsion is turned back in reactor head again and is entered sleeve inner, again flows to agitating vane, forms the logistics of a high-speed circulating.Have recycle stock in this reactor, the reaction times of partial material is longer, and side reaction can increase, and acid consumption is comparatively large, unfavorable to the raising of product octane value.
Disclose the sulfuric acid alkylation reaction process of a kind of C3-C5 alkene and Trimethylmethane, cancel traditional mechanical stirring mode, injector is adopted to mix reaction mass and then react, but in sulfuric acid alkylation reaction process, the density difference of sulfuric acid and hydrocarbon material is comparatively large, and the effect of spraying hybrid mode needs to improve further.US 5,785,933disclosing a kind of sulfuric acid catalysis alkylation reactor system, multiple injection pipeline entrances that inside reactor is put by arranging baffle plate and tangential height, making reaction mass form mix and blend in reactor, and then cancel mechanical moving element.This technology utilizes the principle design of static mixer sulfuric acid alkylation reactor, but mixed effect needs to improve further.
CN1907924A discloses a kind of ionic liquid-catalyzed reaction process and reaction unit, hydrocarbon raw material and ionic-liquid catalyst react in rotary drill reactor, rotating bed is arranged on reactor internal upper part, reactor lower part is container for storing liquid, reactor center arranges whipping appts, and container for storing liquid and feed liquid recycle pump connect and compose rotating bed recirculation reactor.This reactor is not suitable for sulfuric acid process alkylation process, because the heat exchange mode adopted is recycle stock heat-obtaining mode, be unwell to the sulfuric acid process alkylated reaction that heat release is larger, container for storing liquid and the employing reaction mass cyclical operation mode of reactor lower part can increase side reaction.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind of alkylation reaction method of sectional feeding, improve the contact efficiency of catalyzer and hydrocarbon reaction raw material, reduce the acid consumption of sulfuric acid catalyst, reduce temperature of reaction, improve the quality of products.
The invention provides a kind of point of two section feeding alkylation reaction technique methods, comprise the steps:
(1) vitriol oil and Trimethylmethane enter colloidal mill, are thoroughly mixed to form emulsion;
(2) emulsion that step (1) obtains enters alkylation reactor with the hydrocarbon mixture comprising C3 ~ C5 alkene and Trimethylmethane and reacts;
Wherein, step (2) described alkylation reactor comprises reactor shell, end socket, interior rotating bed, outward turning rotated bed, feed-pipe, charging distribution pipe, discharge port, circulating cooling gas entrance, and circulating cooling gas exports, reactor shell and end socket form closed reactor housing, interior rotating bed is vertically set on middle part in housing, interior rotating bed center is empty barrel structure, charging distribution pipe is arranged in the empty barrel structure at interior rotating bed center, charging distribution pipe is communicated with feed-pipe, feed-pipe and end socket junction arrange entry mixers, discharge port is arranged on reactor shell bottom, interior rotating bed is connected with upper drive mechanism by feed-pipe, interior rotating bed radial outside arranges outward turning rotated bed, between interior rotating bed and outward turning rotated bed, there is suitable gap, to be connected to one structure by containment member between interior rotating bed upper end and charging distribution pipe, outward turning rotated bed top is fixedly connected with by containment member with between reactor shell, be between outward turning rotated bed top and two place's containment members and be rotatably connected, outward turning rotated bed is connected with lower part driving device by turning axle, circulating cooling gas entrance and the outlet of circulating cooling gas are separately positioned in the reactor shell of containment member the upper side and lower side.
In alkylation reaction method of the present invention, described alkylation reactor cylindrical shell is preferably cylindrical tube, and end socket comprises upper cover and lower cover, and cylindrical reactor preferred vertical is arranged; Rotating bed comprises interior rotating bed and outward turning rotated bed, and rotating bed preferably adopts corrosion-resistant framework and bed to form, and bed preferably adopts corrosion resistant metal silk screen or filler to form; Rotating bed profile is cylinder barrel shaped, arranges suitable space between outward turning rotated bed and reactor shell, forms annulus; Interior rotating bed center is cylindrical empty cylinder, and charging distribution pipe is arranged in this cylindrical empty cylinder, has suitable space between charging distribution pipe and interior rotating bed, forms annulus; Charging distribution pipe is arranged suitable material distribution hole, the length of material distribution pipe is corresponding with the axial length of rotating bed; Interior rotating bed is with the dead in line of outward turning rotated bed and turning direction is contrary, and the clearance distance between interior rotating bed and outward turning rotated bed is 5mm ~ 300mm, preferred 10mm ~ 50mm.The thickness of interior rotating bed is 0.2 times ~ 1.5 times of outward turning rotated bed thickness, preferably 0.5 times ~ 0.8 times.
In alkylation reaction method of the present invention, feed-pipe one end of described alkylation reactor is communicated with charging distribution pipe, the feed-pipe the other end is connected with drive unit as turning axle, the upper cover junction of feed-pipe and reactor arranges entry mixers, described entry mixers comprises vitriol oil import, liquid hydrocarbon entrance, upper bearing containment member, upper cover mechanical sealing assembly, mechanical seal component and dynamic sealing assembly.
In alkylation reaction method of the present invention, the outward turning rotated bed of described alkylation reactor is connected with drive unit by turning axle, and turning axle is fixedly connected with outward turning rotated bed one end retaining plate, and turning axle preferred vertical is arranged; The drive unit that turning axle is arranged through the outer bottom of lower cover and reactor is connected.
In alkylation reaction method of the present invention, between the circulating cooling gas entrance of described alkylation reactor and the outlet of circulating cooling gas, circulation gas refrigeration system is set; Refrigeration system is arranged on reactor outside, also can be arranged on inside reactor, is preferably the former; Circulating cooling gas formed circulation before refrigeration system and rotating bed, for reaction process provides suitable temperature environment; Circulating cooling gas entrance and circulating cooling gas outlet setting position are one of following two kinds: (1) with the containment member arranged between rotating bed top and reactor shell for boundary, circulating cooling gas entrance is arranged on the housing on containment member top, and the outlet of circulating cooling gas is arranged on the housing of containment member bottom; (2) with the containment member arranged between rotating bed top and reactor shell for boundary, circulating cooling gas entrance is arranged on the housing of containment member bottom, circulating cooling gas outlet be arranged on the housing on containment member top.When adopting aforesaid way (1), circulating cooling gas and reaction mass pass rotating bed in the same way, because rotating bed has suction function to gas, therefore, circulating cooling gas power delivery unit can not be set, or lower-powered circulating cooling gas power delivery unit is set; When adopting aforesaid way (2), circulating cooling gas and reaction mass pass back through rotating bed, need to arrange circulating cooling gas power delivery unit.Therefore, preferred aforesaid way (1).
In alkylation reaction method of the present invention, described alkylation reactor arranges circulating cooling gas refrigeration system, rotating bed is utilized to rotate the tiny structure formed, promote circulating cooling gas phase to realize from the flowing laterally of bed center, when reaction process needs heating or cooling, using circulating cooling gas as the carrier of Cooling and Heat Source, the circulating cooling gas of discharging from the outlet of circulating cooling gas enters hot tube heat exchanger bottom through the gas inlet of hot tube heat exchanger, refrigerant in coolant storage tank enters hot tube heat exchanger top through refrigerant inlet, heat exchange is carried out with heat-pipe elements, heat-pipe elements and refrigerant are after heat exchange, heat-pipe elements temperature reduces, through with refrigerant heat exchange after heat-pipe elements and the circulating cooling gas of hot tube heat exchanger bottom carry out heat exchange, after reaching temperature requirement, alkylation reactor is entered through circulating cooling gas entrance, complete the adjustment to temperature of reaction, with the refrigerant after heat-pipe elements heat exchange through refrigerant exit, and coolant storage tank is entered after cold medium compressor compression.The refrigerant adopted in coolant storage tank is liquefied ammonia, dry ice, hypothermic saline, ethanol etc.
Alkylation reaction method of the present invention, the Trimethylmethane in step (1) and step (2) forms total isobutane feed, and wherein, in step (1), isobutane feed accounts for 30% ~ 80% of total isobutane feed, and preferably 40% ~ 60%.The mol ratio of total Trimethylmethane and C3 ~ C5 alkene is mol ratio is 1:1 ~ 300:1, is preferably 3:1 ~ 50:1.C3 ~ C5 alkene is monoolefine, is preferably butylene.
Alkylation reaction method of the present invention, the sour hydrocarbon volume ratio of the hydrocarbon mixture of the vitriol oil and total Trimethylmethane and C3 ~ C5 alkene is 0.1:1 ~ 5:1, is preferably 0.5:1 ~ 1.5:1; The mass concentration of the vitriol oil is 90% ~ 97%, is preferably 93% ~ 96%.The sulfuric acid of Reaction Separation recycles, and sulfuric acid concentration can supplement the fresh vitriol oil to maintain suitable concentration after reducing.Sulfuric acid concentration is relevant to its zero pour, and in reaction system, the concentration of the vitriol oil needs to mate with temperature of reaction, namely should higher than the zero pour of working concentration sulfuric acid in temperature of reaction.
Alkylation reaction method of the present invention, temperature of reaction is-20 ~ 15 DEG C, is preferably-10 ~ 10 DEG C, most preferably is-5 ~ 5 DEG C.Reaction pressure, to maintain the pressure that hydrocarbon mixture is at the reaction temperatures liquid phase, is generally 0.2 ~ 1.5MPa, is preferably 0.3 ~ 0.8MPa.The rotating speed of rotating bed is generally 50 ~ 5000 revs/min (rpm), is preferably 150 ~ 2000rpm.Reaction mass residence time in reactor is generally 2 ~ 600 seconds, is preferably 10 ~ 100 seconds.
Alkylation reaction method of the present invention, adopt circulating cooling pneumatic control temperature of reaction, circulating cooling gas adopt not with the arbitrary gas of material reaction in reactive system, be preferably nitrogen, hydrogen, rare gas element, carbon monoxide, carbonic acid gas, methane, ethane etc., most preferably be nitrogen or methane.The refrigeration system of circulating cooling gas can use existing any refrigeration system.
Alkylation reaction method of the present invention, reacted material, through sedimentation and follow-up separating step, isolates sulfuric acid, the alkylate oil that reaction generates, and unreacted material etc.Unreacted material such as Trimethylmethane and rare hydrocarbon etc. can recycle.
Compared with prior art, the present invention adopts rotating bed sulfuric acid alkylation method and reacting appliance to have the following advantages:
1, sectional feeding alkylation reaction method of the present invention, adopt the mode that colloidal mill and rotary drill reactor coordinate, sectional feeding reacts, and potent mixing, reinforcing mass transfer, is more suitable for high viscosity operating mode.Adopt jet mixer to realize the pre-mixing of the vitriol oil and part Trimethylmethane material, complete first time two-phase mixtures.Mixed material enters colloidal mill from head-on collision room, and in colloidal mill, material, under powerful shearing force, frictional force and high-frequency vibration effect, effectively by powder emulsification, homogeneous, Wen He, realizes acid hydrocarbon emulsification process.Acid hydrocarbon emulsification liquid and material n-butene and part Trimethylmethane enter rotary drill reactor through material injector, rotary drill reactor mass-transfer efficiency is high, be conducive to high-viscosity material and improve mass-transfer efficiency, realize low-temperature mixed reaction, from rotary drill reactor discharge port outflow reactor, complete mixing mass transfer and reaction.
2, the mode that in rotating bed alkylation reactor adopts, rotating bed coordinates with outward turning rotated bed, realize high-efficient contact during high-viscosity material reaction, speed when material is thrown away lathe by interior rotating bed is higher, there is higher motion capacity, with high speed, fine drop form hits outer rotation bed inwall, because interior rotating bed and outward turning rotated bed are rotate in the other direction, tangential force increases, reinforcing mass transfer and reaction, realize the shock again of two kinds of liquid phases, enhancing mixed effect, fully reaction further, make full use of the kinetic energy in material, when reaching same reaction effect, the power consumption needed reduces.Be conducive to the collection of fog-like liquid material simultaneously.
3, lower temperature of reaction can be adopted.In sulfuric acid process alkylated reaction, temperature of reaction is low has many-sided advantage, is embodied in the octane value, minimizing side reaction, reduction acid consumption etc. that can improve product.Adopt in the sulfuric acid process alkylation techniques of conventional reactor, temperature of reaction is generally 4 ~ 10 DEG C of operations, reason is in existing reactor, and main employing mechanical stirring mode, when temperature of reaction is lower, reaction mass viscosity significantly reduces (mainly the viscosity of the vitriol oil when low temperature is very large), when adopting pre-existing reactors, because the viscosity of the vitriol oil significantly reduces, the vitriol oil and hydrocarbon raw material cannot form sufficient dispersion system, when causing temperature of reaction lower than 5 DEG C, reaction effect is poor.Adopt rotating bed alkylation reactor of the present invention, due to the hypergravity effect that rotating bed produces in rotation process, the large material of viscosity can be made still to obtain sufficient dispersion, the vitriol oil can be realized when lesser temps and the abundant dispersing contact of hydrocarbon raw material, obtain desirable reaction effect.Experiment shows, when the inventive method is below-15 DEG C, still has good reaction effect.
4, the scale of conversion unit reduces greatly.In sulfuric acid process alkylated reaction, Trimethylmethane solubleness is in concentrated sulfuric acid lower, belongs to two phase reaction in addition, and resistance to mass transfer is comparatively large, and speed of response mainly controls by mass transfer step.When adopting existing conversion unit, because two-phase dispersion effect is not enough, speed of response is comparatively slow, and complete identical reaction, required conversion unit is larger.Adopt rotating bed alkylation reactor of the present invention, can reinforcing mass transfer process greatly, speed of response is fast, and the required reaction times is short, and conversion unit scale can reduce greatly, and then reduces equipment cost and process cost.
5, reaction process temperature field reaches the homogeneous of micron order yardstick.Sulfuric acid process alkylated reaction belongs to reactive liquid solution, in traditional reactor, is pure liquid phase reaction, liquid phase is moving material, realize macroscopically temperature of reaction by the strong stirring of liquid phase reacting material even, and due to material viscosity comparatively large, effectively cannot get rid of the reaction focus of local.In the inventive method, adopt circulating cooling gas to be heat-eliminating medium, gas phase is external phase, and liquid phase is disperse phase, and reaction mass is dispersed in circulating cooling medium with atomic little liquid mist, completely different from traditional indirect heat exchange heat-obtaining mode.The inventive method, under the hypergravity effect of rotating bed, reaction mass can be made to realize the dispersion of micron order yardstick, liquid phase material is with small Granular composite in gas phase heat-eliminating medium, and heat interchanging area far operated and uses tube bank to be the reactor connecing heat exchange, and temperature of reaction is more even, do not produce focus, temperature of reaction realizes even on micron order yardstick, and traditional reactor can only realize homogeneous temperature macroscopically, cannot get rid of the focus of local.And focus is the root causing a series of harmful effect, as quality product declines, acid consumption increases.In addition, rotary drill reactor in prior art, does not have suitable temperature control mode, cannot be used for sulfuric acid process alkylation process.
Accompanying drawing explanation
Fig. 1 is alkylation reaction method schematic flow sheet of the present invention.Wherein: 1 is colloidal mill motor, 2 is colloidal mill, and 3 is head-on collision room, 4 is Trimethylmethane entrance, and 5 is vitriol oil entrance, and 6 is spray tube, 23 is pneumatic outlet, and 24 is clapboard of heat pipe exchanger, and 25 is heat-pipe elements, 26 is hot tube heat exchanger, and 27 is coolant injection device, and 28 is refrigerant inlet, 29 is coolant storage tank, and 30 is cold medium compressor, and 31 is hot tube heat exchanger housing, 32 is refrigerant exit, and 33 is gas inlet.
Fig. 2 is alkylation reactor structural representation of the present invention.Wherein, 7 is acid hydrocarbon emulsification liquid entrance, 8 is C3 ~ C5 alkene and Trimethylmethane entrance, 9 is entry mixers, 10 is top shaft coupling, 11 is top drive-motor, 12 is reactor upper cover, 13 is the containment member between interior rotating bed and feed-pipe, 14 is containment member between outer bed and housing, 15 is interior rotating bed, 16 is outward turning rotated bed, 17 is cylindrical shell, 18 is lower cover, 19 is discharge port, 20 is the outlet of circulating cooling gas, 21 is circulating cooling gas entrance, 34 is lower cover mechanical seal, 35 is bottom shaft coupling, 36 is bottom drive-motor, 37 is material distribution pipe, 38 is turning axle.
embodiment
As shown in Figure 1, sectional feeding alkylation reaction method of the present invention, for Trimethylmethane and rare hydrocarbon for raw material, take the vitriol oil as the alkylation process of catalyzer.Utilize the powerful centrifugal force of rotating bed, full-bodied reaction mass is fully disperseed, realize good reaction effect.The equipment of suitable material pre-mixing is set, utilizes charging pump lift to remain, realize the shock of two kinds of liquid phases, enhancing mixed effect.
Mixed material enters colloidal mill from head-on collision room, under the powerful shearing force of colloidal mill, frictional force and high-frequency vibration effect, effectively by powder emulsification, homogeneous, Wen He, realizes acid hydrocarbon emulsification process.Acid hydrocarbon emulsification liquid and supplementary material enter material distribution pipe, and by material dispersion on bed, material, on the bed assembly inwall of high-speed rotation, forms hard hit, realizes enhancing mixed again; In interior rotating bed, the bed assembly highly rotated realizes powerful cutting to material, and liquid phase is drawn as the liquid film of nano-scale dimension or drop or brin, and namely liquid phase surface is greatly upgraded, and then eliminates concentration difference, and reinforcing mass transfer is reacted.At interior rotating bed outer place, mixture is thrown off a body, and hit inner rotary bed inwall with high speed, fine drop form, because interior rotating bed and outward turning rotated bed are rotate in the other direction, tangential force increases, reinforcing mass transfer and reaction again, the high speed rotating of outward turning rotated bed realizes powerful cutting to material again, and liquid phase is drawn as the liquid film of nano-scale dimension or drop or brin, and namely liquid phase surface is greatly upgraded again, and then elimination concentration difference, continue reinforcing mass transfer reaction.Rotating bed layer assembly outer place outside, mixture is thrown off forms, strikes reactor shell inwall, collects reactor lower cover under gravity, by material outlet outflow reactor, so far completes reactive liquid solution process.
In reactor operation process, rotating bed is utilized to rotate the hypergravity effect formed, liquid phase material is disperseed, utilize liquid phase material to the suction function of gas phase, promote gas phase to realize from the flowing laterally of bed center, realizing with gas phase is continuous print heat-eliminating medium, to the abundant effective cooling of the liquid phase of high dispersing, realizes the high uniformity in temperature field.
Head-on collision is indoor arranges relative spray tube, spray tube is made up of several nozzles, and nozzle total sectional area is 1/3 ~ 4/5 of charging pipe connecting sectional area, and liquid hydrocarbon spray tube overlaps with vitriol oil spray tube horizontal axis, nozzle is corresponding, to ensure good head-on collision dispersion effect.
Below in conjunction with embodiment, reaction effect of the present invention is described, but does not therefore limit the scope of the invention.
Embodiment 1 ~ 3
Adopt the reactor of structure as shown in Figure 1, the bed of rotating bed is made up of Stainless Steel Cloth filler, and the bed voidage of Stainless Steel Cloth filler is 0.95, and specific surface area is 4000m 2/ m 3, wire diameter is 1mm, rotates bed volume and accounts for 45% of rotary drill reactor cubic capacity.Interior rotating bed is with the dead in line of outward turning rotated bed and turning direction is contrary, and the clearance distance between interior rotating bed and outward turning rotated bed is 50mm, and the thickness of interior rotating bed is 0.5 times of outward turning rotated bed thickness.
Take mass concentration as the vitriol oil of 95% be catalyzer, with Trimethylmethane and butylene for raw material carries out alkylated reaction.
The mol ratio of isobutane feed and vitriol oil charging in colloidal mill is 10:1 ~ 2:1, is preferably 6:1 ~ 4:1.The mol ratio of supplementing isobutane and butene in material inlet is 1:1 ~ 100:1, is preferably 3:1 ~ 20:1.The mol ratio of total isobutane and butene is 1:1 ~ 300:1, is preferably 3:1 ~ 50:1.Acid hydrocarbon volume ratio is 0.1:1 ~ 5:1, is preferably 0.5:1 ~ 1.5:1.Temperature of reaction is-20 ~ 15 DEG C, is preferably-10 ~ 10 DEG C, most preferably is-5 ~ 5 DEG C.Reaction pressure is 0.2 ~ 1.5MPa, is preferably 0.3 ~ 0.8MPa.The rotating speed of rotating bed is generally 50 ~ 5000 revs/min (rpm), is preferably 150 ~ 2000rpm.The reaction time of reaction mass in reactor is generally 1 ~ 600 second, is preferably 10 ~ 100 seconds.
In alkylated reaction of the present invention, circulating cooling gas adopts nitrogen, and the refrigeration system of circulating cooling gas uses ammonia refrigeration system.
Concrete operations condition is in table 1, and reaction result is in table 2.
Comparative example
Adopt conventional inside that the horizontal mechanical stirred reactor (structure is see shown in 02 phase " the alkylating process unit of isobutane and butene is summarized " one texts and pictures 2 in 2002 such as Liu Zhigang " Sweet natural gas and oil ") of refrigeration tube bank is set, reaction conditions is see the optimized commercial operating conditions in table 1(this area), reaction result is see table 2.
Table 1 embodiment and comparative example alkylated reaction underlying condition
Table 2 embodiment and comparative example alkylated reaction result
As can be seen from above-described embodiment and comparative example, alkylation reactor of the present invention has small scale, and acid consumption is low, quality product high.

Claims (19)

1. a sectional feeding alkylation reaction method, comprises the steps:
(1) vitriol oil and Trimethylmethane enter colloidal mill, are thoroughly mixed to form emulsion;
(2) emulsion that obtains of step (1) and Trimethylmethane and the hydrocarbon mixture that comprises C3 ~ C5 alkene enter alkylation reactor and react;
Wherein, step (2) described alkylation reactor comprises reactor shell, end socket, interior rotating bed, outward turning rotated bed, feed-pipe, charging distribution pipe, discharge port, circulating cooling gas entrance, and circulating cooling gas exports, reactor shell and end socket form closed reactor housing, interior rotating bed is vertically set on middle part in housing, interior rotating bed center is empty barrel structure, charging distribution pipe is arranged in the empty barrel structure at interior rotating bed center, charging distribution pipe is communicated with feed-pipe, feed-pipe and end socket junction arrange entry mixers, discharge port is arranged on reactor shell bottom, interior rotating bed is connected with upper drive mechanism by feed-pipe, interior rotating bed radial outside arranges outward turning rotated bed, between interior rotating bed and outward turning rotated bed, there is suitable gap, to be connected to one structure by containment member between interior rotating bed upper end and charging distribution pipe, outward turning rotated bed top is fixedly connected with by containment member with between reactor shell, be between outward turning rotated bed top and two place's containment members and be rotatably connected, outward turning rotated bed is connected with lower part driving device by turning axle, circulating cooling gas entrance and the outlet of circulating cooling gas are separately positioned in the reactor shell of containment member the upper side and lower side.
2. alkylation reaction method according to claim 1, is characterized in that: in alkylation reactor, feed-pipe one end is communicated with charging distribution pipe, the outlet of the feed-pipe the other end and jet mixer.
3. alkylation reaction method according to claim 2, it is characterized in that: jet mixer comprises head-on collision room and charging jet orifice, two charging jet orifices that the indoor setting position that clashes is relative, formed between two charging jet orifices and spray mixing zone, utilize the excess power of transferpump to realize the pre-mixing of material.
4. alkylation reaction method according to claim 1, is characterized in that: in alkylation reactor, and reactor shell is cylindrical tube, and end socket comprises upper cover and lower cover, and cylindrical reactor is vertically arranged.
5. alkylation reaction method according to claim 1, is characterized in that: in alkylation reactor, and rotating bed adopts corrosion-resistant framework and bed to form, and bed adopts corrosion resistant metal silk screen or filler to form; Rotating bed profile is cylinder barrel shaped, arranges suitable space between outward turning rotated bed and reactor shell, forms annulus; Interior rotating bed center is cylindrical empty cylinder, and charging distribution pipe is arranged in this cylindrical empty cylinder, has suitable space between charging distribution pipe and interior rotating bed, forms annulus; Charging distribution pipe is arranged suitable material distribution hole, the length of charging distribution pipe is corresponding with the axial length of rotating bed; Outward turning rotated bed is connected with drive unit by turning axle, and turning axle is fixedly connected with outward turning rotated bed one end retaining plate, and turning axle preferred vertical is arranged; The drive unit that turning axle is arranged through the outer bottom of lower cover and reactor is connected.
6. alkylation reaction method according to claim 1, is characterized in that: in alkylation reactor, arranges circulation gas refrigeration system between circulating cooling gas entrance and the outlet of circulating cooling gas; Circulation gas refrigeration system is arranged on reactor outside, or is arranged on inside reactor.
7. alkylation reaction method according to claim 6, is characterized in that: circulating cooling gas formed circulation before circulation gas refrigeration system and rotating bed, for reaction process provides suitable temperature environment; Circulating cooling gas entrance and circulating cooling gas outlet setting position are one of following two kinds: (1) with the containment member arranged between rotating bed top and reactor shell for boundary, circulating cooling gas entrance is arranged on the housing on containment member top, and the outlet of circulating cooling gas is arranged on the housing of containment member bottom; (2) with the containment member arranged between rotating bed top and reactor shell for boundary, circulating cooling gas entrance is arranged on the housing of containment member bottom, circulating cooling gas outlet be arranged on the housing on containment member top.
8. alkylation reaction method according to claim 7, is characterized in that: arrange circulating cooling gas power delivery unit.
9. alkylation reaction method according to claim 1, is characterized in that: interior rotating bed is with the dead in line of outward turning rotated bed and turning direction is contrary.
10. alkylation reaction method according to claim 1, is characterized in that: the clearance distance between interior rotating bed and outward turning rotated bed is 5mm ~ 300mm, preferred 10mm ~ 50mm.
11. alkylation reaction methods according to claim 1, is characterized in that: the thickness of interior rotating bed is 0.2 times ~ 1.5 times of outward turning rotated bed thickness, preferably 0.5 times ~ 0.8 times.
12. alkylation reaction methods according to claim 1, it is characterized in that: the Trimethylmethane in step (1) and step (2) forms total isobutane feed, wherein, isobutane feed accounts for 30% ~ 80% of total isobutane feed in step (1), and preferably 40% ~ 60%.
13. alkylation reaction methods according to claim 1, is characterized in that: the mol ratio of total Trimethylmethane and C3 ~ C5 alkene is mol ratio is 1:1 ~ 300:1, is preferably 3:1 ~ 50:1.
14. alkylation reaction methods according to claim 1, is characterized in that: the sour hydrocarbon volume ratio of the hydrocarbon mixture of the vitriol oil and total Trimethylmethane and C3 ~ C5 alkene is 0.1:1 ~ 5:1, are preferably 0.5:1 ~ 1.5:1; The mass concentration of the vitriol oil is 90% ~ 97%, is preferably 93% ~ 96%.
15. alkylation reaction methods according to claim 1, is characterized in that: in alkylated reaction, and temperature of reaction is-20 ~ 15 DEG C, are preferably-10 ~ 10 DEG C, most preferably are-5 ~ 5 DEG C; Reaction pressure, to maintain the pressure that hydrocarbon mixture is at the reaction temperatures liquid phase, is preferably 0.2 ~ 1.5MPa, most preferably is 0.3 ~ 0.8MPa.
16. alkylation reaction methods according to claim 1, is characterized in that: the rotating speed of alkylation reactor rotating bed is 50 ~ 5000 revs/min, are preferably 150 ~ 2000 revs/min.
17. alkylation reaction methods according to claim 1, is characterized in that: reaction mass residence time in reactor is 1 ~ 600 second, are preferably 10 ~ 100 seconds.
18. alkylation reaction methods according to claim 1, is characterized in that: in alkylated reaction, adopt circulating cooling pneumatic control temperature of reaction, circulating cooling gas adopt not with the arbitrary gas of material reaction in reactive system.
19. alkylation reaction methods according to claim 16, is characterized in that: circulating cooling gas is nitrogen, hydrogen, rare gas element, carbon monoxide, carbonic acid gas, methane or ethane.
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