CN104549114B - A kind of method of alkylation reactor and alkylated reaction - Google Patents
A kind of method of alkylation reactor and alkylated reaction Download PDFInfo
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- B01J19/26—Nozzle-type reactors, i.e. the distribution of the initial reactants within the reactor is effected by their introduction or injection through nozzles
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- 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
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- 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
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- 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
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- C10G2300/1088—Olefins
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Abstract
The invention discloses a kind of alkylation reactor and alkylation reaction method, including reactor shell, end socket, interior revolving bed, outward turning rotated bed, feed pipe, charging distributor pipe, discharging opening, circulating cooling gas entrance and exit；Reactor shell and end socket are constituted closes housing, in the middle part of interior revolving bed is arranged in housing, charging distributor pipe is arranged in the sky barrel structure of interior revolving bed center, charging distributor pipe connects with feed pipe, feed pipe and end socket junction arrange entry mixers, discharging opening is located at lower housing portion, interior revolving bed is connected with driving device by feed pipe, interior revolving bed arranged outside outward turning rotated bed, structure is connected as one by containment member between interior revolving bed upper end and charging distributor pipe, fix between outward turning rotated bed and housing and be connected, outward turning rotated bed is connected with lower part driving device by rotating shaft。Alkylation of the present invention, with concentrated sulphuric acid for catalyst, enters and alkylated reaction with iso-butane and alkene for raw material, and reaction can carry out at low temperatures, and acid consumption is low, and product quality is high。
Description
Technical field
The present invention relates to a kind of alkylation reactor and alkylation reaction method, specifically a kind of alkylation reactor adopting iso-butane and C3～C5 olefin catalytic alkylated reaction and alkylation reaction method。
Background technology
Along with the fast development of economic development, particularly transportation, the discharge of Vehicular exhaust is one of air-polluting main source, and improving quality of gasoline is reduce the main approach that Vehicular exhaust pollutes。The alkylate oil that the alkylated reaction of iso-butane and C3～C5 alkene obtains, has without features such as sulfur, high-octane rating height, research octane number (RON) and motor octane number difference are little, is the important blend component of high-quality clean gasoline。
Alkylated reaction is the conventional art in petroleum refining field, mainly has sulfuric acid process alkylation techniques and hydrogen fluoride alkylation techniques, and under the effect of catalyst (sulphuric acid or Fluohydric acid .), isobutane and olefins is obtained by reacting isoparaffin。Sulfuric acid process alkylation is compared with hydrogen fluoride alkylation, differs from one another in technique, is also all sufficiently close to from aspects such as capital expenditure, production cost, product yield and product qualities, therefore both approaches energy long-term co-existence, is all widely adopted。On the whole, from the yield of the quantity of alkyl plant and alkyl oil, current hydrofluoric acid alkylation unit is dominant, but the increasingly stringent required recently as environmental regulation and the hypertoxic characteristic of Fluohydric acid., new device many employings alkyl sodium sulfate metallization processes。
In sulfuric acid process alkylation techniques, reaction carries out at relatively low temperature, and reaction unit needs have refrigerating function。In hydrogen fluoride alkylation techniques, reaction temperature is of a relatively high, is generally adopted water-cooled and namely can meet reaction requirement。Therefore, both reactor assembly differences are bigger。Traditional sulfuric acid process alkylation reactor structure species is more, and currently used more have two kinds, and one is cascade sulfuric acid alkylation reaction unit, and one is Stratco formula reactor (i.e. the internal indirect refrigeration reactor arranging heat-obtaining tube bank)。
The reactor of cascade sulfuric acid alkylation device is generally made up of several conversion zones, the intersegmental overflow baffle of each reaction separates, each conversion zone is equipped with agitator, product and sulphuric acid and finally enters settling section and be easily separated, and the sulphuric acid circulating pump separated is sent into conversion zone and reused。Adopt reactant iso-butane spontaneous evaporation refrigeration, the advantage of this response system be alkane alkene in each conversion zone than high, power consumption is little, do not need another refrigerant feeding。But owing to alkane and alkene are not pre-mixed, thus reduce the quality of alkylate oil, add acid consumption。And influencing each other between each conversion zone, a conversion zone operation is abnormal, and whole reactor is affected by impact。
It is that to adopt be horizontal eccentric reactor that inside arranges a kind of concrete structure of indirect refrigeration reactor of heat-obtaining tube bank, the shell of reactor is a horizontal pressure vessel, internal equipped with a powerful agitator, internal recycle sleeve and heat-obtaining tube bank, hydrocarbon raw material is entered reactor by upper and lower two feed pipes, reactor is sprayed into towards impeller after converging before agitator arm, 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, so that sulphuric acid obtains reasonable dispersion with hydro carbons and mixes。Acid hydrocarbon emulsion is turned back entrance sleeve inner in reactor head again, again flows to stirring vane, forms the logistics of a high-speed circulating。Having recycle stock in this reactor, the response time of partial material is longer, and side reaction can increase, and acid consumption is relatively big, and the raising of product octane number is unfavorable。
Disclose the sulfuric acid alkylation course of reaction of a kind of C3-C5 alkene and iso-butane, cancel traditional mechanical agitation mode, ejector is adopted reaction mass to be mixed and then reacts, but in sulfuric acid alkylation course of reaction, sulphuric acid is relatively big with the density contrast of hydrocarbon material, and the effect of injection hybrid mode need to improve further。US5,785,933 disclose a kind of sulfuric acid catalysis alkylation reactor system, and inside reactor, by the multiple injection pipeline entrances arranging baffle plate and tangential height is put, makes reaction mass form mix and blend and then cancellation mechanical moving element in reactor。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, revolving bed is arranged on reactor internal upper part, reactor lower part is fluid reservoir, reactor center arranges agitating device, and fluid reservoir and feed liquid circulating pump connect and compose revolving 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, it is unsuitable for the sulfuric acid process alkylated reaction that heat release is bigger, the fluid reservoir of reactor lower part and employing reaction mass circulation mode of operation and can increase side reaction。
Summary of the invention
For the deficiencies in the prior art, the present invention provides a kind of alkylation reactor and alkylation process, improves the contacting efficiency of catalyst and hydrocarbon reaction raw material, reduces the acid consumption of sulfuric acid catalyst, reduces reaction temperature, improve product quality。
Alkylation reactor of the present invention includes following content: reactor shell, end socket, interior revolving bed, outward turning rotated bed, feed pipe, charging distributor pipe, discharging opening, circulating cooling gas entrance, and circulating cooling gas exports；Reactor shell and end socket constitute closed reactor housing, in the middle part of interior revolving bed is vertically set in housing, interior revolving bed center is empty barrel structure, charging distributor pipe is arranged in the empty barrel structure at interior revolving bed center, charging distributor pipe connects with feed pipe, feed pipe and end socket junction arrange entry mixers, discharging opening is arranged on reactor shell bottom, interior revolving bed is connected with upper drive mechanism by feed pipe, interior revolving bed radial outside arranges outward turning rotated bed, there is between interior revolving bed and outward turning rotated bed suitable gap, it is connected to one structure by containment member between interior revolving bed upper end and charging distributor pipe, it is connected by containment member is fixing between outward turning rotated bed top and reactor shell, it is between outward turning rotated bed top and two place's containment members and is rotatably connected, outward turning rotated bed is connected with lower part driving device by rotating shaft, 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 reactor of the present invention, the preferably cylindrical cylinder of reactor shell, end socket includes upper cover and low head, and cylindrical reactor preferred vertical is arranged；Revolving bed includes interior revolving bed and outward turning rotated bed, and revolving bed preferably employs corrosion-resistant framework and bed is constituted, and bed preferably employs corrosion resistant metal silk screen or filler is constituted；Revolving bed profile is cylinder barrel shaped, arranges suitable space between outward turning rotated bed and reactor shell, forms annulus；Interior revolving bed center is cylindrical empty cylinder, and charging distributor pipe is arranged in this cylindrical empty cylinder, has suitable space between charging distributor pipe and interior revolving bed, forms annulus；Arranging suitable material distribution hole on charging distributor pipe, the length of material distributor pipe is corresponding with the axial length of revolving bed；Interior revolving bed is contrary with outward turning rotated bed dead in line and rotation direction, and the clearance distance between interior revolving bed and outward turning rotated bed is 5mm～300mm, it is preferable that 10mm～50mm。The thickness of interior revolving bed is 0.2 times～1.5 times of outward turning rotated bed thickness, it is preferable that 0.5 times～0.8 times。
In alkylation reactor of the present invention, feed pipe one end connects with charging distributor pipe, the feed pipe other end is connected with driving device as rotating shaft, the upper cover junction of feed pipe and reactor arranges entry mixers, described entry mixers includes concentrated sulphuric acid import, liquid hydrocarbon entrance, upper bearing containment member, upper cover mechanical sealing assembly, mechanical seal component and dynamic sealing assembly。
In alkylation reactor of the present invention, outward turning rotated bed is connected with driving device by rotating shaft, and rotating shaft is fixing with the fixing plate in outward turning rotated bed one end to be connected, and rotating shaft preferred vertical is arranged；The driving device that rotating shaft is arranged through the outer bottom of low head and reactor is connected。
In alkylation reactor of the present invention, between circulating cooling gas entrance and the outlet of circulating cooling gas, circulating air refrigeration system is set；Refrigeration system is arranged on outside reactor, it is also possible to be arranged on inside reactor, it is preferred to the former；Circulating cooling gas is previously formed circulation in refrigeration system and revolving bed, provides suitable temperature environment for course of reaction；It is one of following two that circulating cooling gas entrance and the outlet of circulating cooling gas arrange position: (1) is with the containment member of setting between revolving 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) so that between revolving bed top and reactor shell, the containment member of setting is for boundary, circulating cooling gas entrance is arranged on the housing of containment member bottom, and the outlet of circulating cooling gas is arranged on the housing on containment member top。When adopting aforesaid way (1), circulating cooling gas and reaction mass are in the same direction through revolving bed, owing to gas is had swabbing action by revolving bed, therefore, circulating cooling gas power delivery unit can be not provided with, 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 revolving bed, it is necessary to arrange circulating cooling gas power delivery unit。It is therefore preferable that aforesaid way (1)。
Alkylation of the present invention, adopts abovementioned alkyl reactor of the present invention, with iso-butane and C3～C5 alkene for raw material, with sulphuric acid for catalyst, is alkylated and is obtained by reacting alkylate oil。
In alkylated reaction of the present invention, being total hydrocarbon feed by iso-butane and C3～C5 olefin, the mol ratio of iso-butane and C3～C5 alkene is mol ratio is 1:1～300:1, it is preferred to 3:1～50:1。C3～C5 alkene is monoolefine, it is preferred to butylene。
In alkylated reaction of the present invention, catalyst sulfuric acid is concentrated sulphuric acid, and the sour hydrocarbon volume ratio of the hydrocarbon mixture of concentrated sulphuric acid and iso-butane and C3～C5 alkene is 0.1:1 ~ 5:1, it is preferred to 0.5:1 ~ 1.5:1。The mass concentration of concentrated sulphuric acid is 90%～97%, it is preferred to 93%～96%, and the sulphuric acid of Reaction Separation recycles, after sulfuric acid concentration reduces, it is possible to supplement fresh concentrated sulphuric acid to maintain suitable concentration。Sulfuric acid concentration is relevant to its freezing point, and in reaction system, the concentration of concentrated sulphuric acid needs to mate with reaction temperature, namely should be higher than that the freezing point of working concentration sulphuric acid in reaction temperature。
In alkylated reaction of the present invention, reaction temperature is-20～15 DEG C, it is preferred to-10～10 DEG C, it is most preferred that for-5～5 DEG C。Reaction pressure, to maintain the pressure that hydrocarbon mixture is liquid phase at the reaction temperatures, is generally 0.2 ~ 1.5MPa, it is preferred to 0.3 ~ 0.8MPa。The rotating speed of revolving bed is generally 50～5000 revs/min (rpm), it is preferred to 150～2000rpm。Reaction mass time of staying in reactor is generally 2～600 seconds, it is preferred to 10～100 seconds。
In alkylated reaction of the present invention, adopt circulating cooling gas control reaction temperature, circulating cooling gas adopt not with the arbitrary gas of material reaction in response system, it is preferred to nitrogen, hydrogen, noble gas, carbon monoxide, carbon dioxide, methane, ethane etc., it is most preferred that for nitrogen or methane。The refrigeration system of circulating cooling gas can use existing any refrigeration system。
In alkylated reaction of the present invention, reacted material, through sedimentation and follow-up separating step, isolates sulphuric acid, the alkylate oil that reaction generates, and unreacted material etc.。Unreacted material such as iso-butane and rare hydrocarbon etc. can recycle。
Compared with prior art, the present invention adopts revolving bed sulfuric acid alkylation method and reactor to have the advantage that
1. can adopt less reaction temperature。In sulfuric acid process alkylated reaction, reaction temperature is low has many-sided advantage, be embodied in can improve product octane number, reduce side reaction, reduce acid consumption etc.。Adopt in the sulfuric acid process alkylation techniques of conventional reactor, reaction temperature is generally 4～10 DEG C of operations, reason is in existing reactor, and main employing mechanical agitation mode, when reaction temperature is relatively low, reaction mass viscosity significantly increases (mainly the concentrated sulphuric acid viscosity when low temperature is very big), when adopting pre-existing reactors, owing to the viscosity of concentrated sulphuric acid significantly increases, concentrated sulphuric acid and hydrocarbon raw material cannot form sufficient dispersion, when causing reaction temperature lower than 5 DEG C, reaction effect is poor。Adopt the revolving bed alkylation reactor of the present invention, due to the hypergravity effect that revolving bed produces in rotation process, the material that viscosity is big can be made still to obtain sufficient dispersion, it is possible to achieve concentrated sulphuric acid is fully dispersed with hydrocarbon raw material when lower temperature to be contacted, and obtains desirable reaction effect。Experiments show that, when the inventive method is below-15 DEG C, still there is good reaction effect。
2. the scale of consersion unit is greatly reduced。In sulfuric acid process alkylated reaction, iso-butane dissolubility in concentrated sulfuric acid is relatively low, belongs to two phase reaction in addition, and resistance to mass tranfer is relatively big, and response speed is limited mainly by mass transfer step and controls。When adopting existing consersion unit, owing to biphase dispersion effect is not enough, response speed is relatively slow, completes identical reaction, and required consersion unit is larger。Adopting the revolving bed alkylation reactor of the present invention, it is possible to significantly strengthen mass transport process, response speed is fast, and the required response time is short, and consersion unit scale can be substantially reduced, and then reduces equipment cost and operating cost。
3. course of reaction temperature field reaches the homogeneous of micron order yardstick。Sulfuric acid process alkylated reaction belongs to reactive liquid solution, in traditional reactor, for pure liquid phase reactor, liquid phase is moving material, macroscopically reaction temperature is realized uniform by the strong stirring of liquid phase reacting material, and owing to material viscosity is bigger, it is impossible to effectively get rid of the reaction focus of local。In the inventive method, adopting circulating cooling gas is cooling medium, and gas phase is continuous phase, and liquid phase is dispersion phase, and reaction mass is dispersed in circulating cooling medium with atomic little liquid mist, entirely different with traditional indirect heat exchange heat-obtaining mode。The inventive method, under the hypergravity effect of revolving 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 cooling medium, and it is the reactor connecing heat exchange that heat exchange area far operated use tube bank, and reaction temperature is more uniform, do not produce focus, reaction temperature realizes uniform on micron order yardstick, and traditional reactor can only realize homogeneous temperature macroscopically, it is impossible to get rid of the focus of local。And focus is the root causing a series of adverse effect, as product quality declines, acid consumption increase etc.。It addition, rotary drill reactor in prior art, it does not have suitable temperature control mode, it is impossible to for sulfuric acid process alkylation process。
4. the revolving bed alkylation reactor of the present invention is more suitable for sulfuric acid process alkylated reaction。Such as: adopt ejector mixing that concentrated sulphuric acid and hydrocarbon material are carried out premixing, utilize charging pump lift to remain, it is achieved the shock of two kinds of liquid phases, strengthen mixed effect；The liquid phase material swabbing action to gas phase when utilizing revolving bed to operate, it is achieved the circulation of circulating cooling medium, equipment is simple。The flexible operation of the inventive method, operable wide ranges, it is possible to adapt to different operating conditions。
5. revolving bed alkylation reactor adopts the mode that interior revolving 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 revolving bed is higher, there is higher motion capacity, with at a high speed, fine drop form hits outer rotation bed inwall, because interior revolving bed and outward turning rotated bed are that opposite direction rotates, tangential force increases, strengthening mass transfer and reaction, realize the shock again of two kinds of liquid phases, strengthening 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。
Accompanying drawing explanation
Fig. 1 is alkylation reactor structural representation of the present invention。Wherein: 1 is motor, 2 is top shaft coupling, and 3 is biphase material mixer, and 4 is liquid hydrocarbon entrance, 5 is upper cover, 6 is the containment member between interior revolving bed and feed pipe, and 7 is containment member between outer bed and housing, and 8 is interior revolving bed, 9 is outward turning rotated bed, 10 is cylinder, and 11 is low head, and 12 is low head mechanical seal, 13 is bottom shaft coupling, 14 is bottom drive motor, and 15 is discharging opening, and 16 is circulating cooling gas entrance, 17 is charging distributor pipe, 18 export for circulating cooling gas, and 19 is feed pipe, and 20 is concentrated sulphuric acid entrance。
Fig. 2 is entry mixers structural representation。21 is upper bearing containment member, and 22 is upper cover mechanical seal component, and 23 is mechanical sealing assembly, and 24 is dynamic sealing assembly。
Detailed description of the invention
As it is shown in figure 1, alkylation reactor structure of the present invention is percussion flow-rotary drill reactor, it is used for concentrated sulphuric acid for catalyst, the alkylation process being raw material with iso-butane and rare hydrocarbon。Utilize the powerful centrifugal force of revolving bed, by fully dispersed for full-bodied reaction mass, it is achieved good reaction effect。The equipment of suitable material premixing is set, utilizes charging pump lift to remain, it is achieved the shock of two kinds of liquid phases, strengthen mixed effect。
In reactor operation process, revolving bed is utilized to rotate the hypergravity effect formed, liquid phase material is made to disperse, utilize the liquid phase material swabbing action to gas phase, gas phase is promoted to realize from bed center flowing laterally, realize with gas phase for continuous print cooling medium, the liquid phase of high degree of dispersion is fully effectively cooled down, it is achieved the high uniformity in temperature field。
Mixed material enters material distributor pipe from head-on collision room, and by material dispersion to bed, material, on the bed assembly inwall of high-speed rotation, forms hard hit, it is achieved strengthening mixing again；In interior revolving bed, material is realized brute force cutting by the bed assembly highly rotated, and liquid phase is drawn as the liquid film of nano-scale dimension or drop or brin, and namely liquid phase surface is greatly updated, and then eliminates concentration difference, strengthens mass transfer reaction。At interior revolving bed outer place, mixed material is thrown off bed body, and hit external rotation bed inwall with high speed, fine drop form, because interior revolving bed and outward turning rotated bed are that opposite direction rotates, tangential force increases, strengthening mass transfer and reaction again, material is realized brute force cutting by the high speed rotating of outward turning rotated bed 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 updated again, and then elimination concentration difference, continue strengthening mass transfer reaction。Revolving bed layer assembly outer place outside, mixed material is thrown off forms, strikes reactor shell inwall, collects reactor low head under gravity, by material outlet outflow reactor, so far completes reactive liquid solution process。
Head-on collision indoor arrange relative playpipe, playpipe is made up of several nozzles, nozzle total sectional area is the 1/3 ~ 4/5 of charging connecting tube sectional area, liquid hydrocarbon playpipe overlaps with concentrated sulphuric acid playpipe horizontal axis, nozzle is corresponding, utilizes charging pump lift to remain, it is achieved the shock of two kinds of liquid phases, strengthening mixed effect, to ensure good head-on collision dispersion effect。
The reaction effect of the present invention is described below in conjunction with embodiment, but does not therefore limit the scope of the invention。
Embodiment 1～3
Adopting the reactor of structure as shown in Figure 1, the bed of revolving 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 4000m2/m3, wire diameter is 1mm, rotates bed volume and accounts for the 45% of rotary drill reactor total measurement (volume)。Interior revolving bed is contrary with outward turning rotated bed dead in line and rotation direction, and the clearance distance between interior revolving bed and outward turning rotated bed is 50mm, and the thickness of interior revolving bed is 0.5 times of outward turning rotated bed thickness。
With mass concentration be 95% concentrated sulphuric acid for catalyst, be alkylated reaction with iso-butane and butylene for raw material。
The mol ratio of isobutane and butene is 1:1～300:1, it is preferred to 3:1～50:1。Acid hydrocarbon volume ratio is 0.1:1 ~ 5:1, it is preferred to 0.5:1 ~ 1.5:1。Reaction temperature is-20～15 DEG C, it is preferred to-10～10 DEG C, it is most preferred that for-5～5 DEG C。Reaction pressure is 0.2 ~ 1.5MPa, it is preferred to 0.3 ~ 0.8MPa。The rotating speed of revolving bed is generally 50～5000 revs/min (rpm), it is preferred to 150～2000rpm。Reaction mass time of staying in reactor is generally 2～600 seconds, it is preferred to 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 referring to shown in 02 phase in 2002 such as Liu Zhigang " natural gas and oil " " the alkylating process unit summary of isobutane and butene " texts and pictures 2) of refrigeration tube bank is set, reaction condition is referring to the optimized commercial operating conditions in table 1(this area), reaction result is referring to table 2。
Table 1 embodiment and comparative example alkylated reaction essential condition
Table 2 embodiment and comparative example alkylated reaction result
From the above with comparative example it can be seen that alkylation reactor of the present invention has small scale, acid consumption is low, product quality high。
Claims (28)
1. an alkylation reactor, it is characterised in that including reactor shell, end socket, interior revolving bed, outward turning rotated bed, feed pipe, charging distributor pipe, discharging opening, circulating cooling gas entrance, circulating cooling gas exports；Reactor shell and end socket constitute closed reactor housing, in the middle part of interior revolving bed is vertically set in housing, interior revolving bed center is empty barrel structure, charging distributor pipe is arranged in the empty barrel structure at interior revolving bed center, charging distributor pipe connects with feed pipe, feed pipe and end socket junction arrange entry mixers, discharging opening is arranged on reactor shell bottom, interior revolving bed is connected with upper drive mechanism by feed pipe, interior revolving bed radial outside arranges outward turning rotated bed, there is between interior revolving bed and outward turning rotated bed suitable gap, it is connected to one structure by containment member between interior revolving bed upper end and charging distributor pipe, it is connected by containment member is fixing between outward turning rotated bed top and reactor shell, it is between outward turning rotated bed top and two place's containment members and is rotatably connected, outward turning rotated bed is connected with lower part driving device by rotating shaft, 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. reactor according to claim 1, it is characterised in that: in alkylation reactor, feed pipe one end connects with charging distributor pipe, the outlet of the feed pipe other end and ejector mixing。
3. reactor according to claim 2, it is characterized in that: ejector mixing includes head-on collision room and charging jet, head-on collision indoor arrange two charging jets that position is relative, form injection mixed zone, it is achieved the premixing of material between two charging jets。
4. reactor according to claim 1, it is characterised in that: in alkylation reactor, reactor shell is cylindrical tube, and end socket includes upper cover and low head, and cylindrical reactor is vertically arranged。
5. reactor according to claim 4, it is characterised in that: in alkylation reactor, revolving bed adopts corrosion-resistant framework and bed to constitute, and bed adopts corrosion resistant metal silk screen or filler to constitute；Revolving bed profile is cylinder barrel shaped, arranges suitable space between outward turning rotated bed and reactor shell, forms annulus；Interior revolving bed center is cylindrical empty cylinder, and charging distributor pipe is arranged in this cylindrical empty cylinder, has suitable space between charging distributor pipe and interior revolving bed, forms annulus；Arranging suitable material distribution hole on charging distributor pipe, the length of charging distributor pipe is corresponding with the axial length of interior revolving bed；Outward turning rotated bed is connected with lower part driving device by rotating shaft, and rotating shaft is fixing with the fixing plate in outward turning rotated bed one end to be connected, and the driving device that rotating shaft is arranged through the outer bottom of low head and reactor is connected。
6. reactor according to claim 5, it is characterised in that: rotating shaft is vertically arranged。
7. reactor according to claim 1, it is characterised in that: in alkylation reactor, between circulating cooling gas entrance and the outlet of circulating cooling gas, circulating air refrigeration system is set；Circulating air refrigeration system is arranged on outside reactor, or is arranged on inside reactor。
8. reactor according to claim 7, it is characterised in that: circulating cooling gas is previously formed circulation in circulating air refrigeration system and revolving bed, provides suitable temperature environment for course of reaction；It is one of following two that circulating cooling gas entrance and the outlet of circulating cooling gas arrange position: the containment member arranged between revolving bed top and reactor shell beyond (1) is 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) containment member arranged between revolving bed top and reactor shell beyond is boundary, and circulating cooling gas entrance is arranged on the housing of containment member bottom, and the outlet of circulating cooling gas is arranged on the housing on containment member top。
9. reactor according to claim 8, it is characterised in that: circulating cooling gas power delivery unit is set。
10. reactor according to claim 1, it is characterised in that: interior revolving bed is contrary with outward turning rotated bed dead in line and rotation direction。
11. the reactor according to claim 1 or 10, it is characterised in that: the clearance distance between interior revolving bed and outward turning rotated bed is 5mm～300mm。
12. reactor according to claim 11, it is characterised in that: the clearance distance between interior revolving bed and outward turning rotated bed is 10mm～50mm。
13. the reactor according to claim 1 or 10, it is characterised in that: the thickness of interior revolving bed is 0.2 times～1.5 times of outward turning rotated bed thickness。
14. reactor according to claim 13, it is characterised in that: the thickness of interior revolving bed is 0.5 times～0.8 times of outward turning rotated bed thickness。
15. an alkylation, with iso-butane and C3～C5 alkene for raw material, with sulphuric acid for catalyst, it is alkylated and is obtained by reacting alkylate oil, it is characterised in that: use the alkylation reactor described in claim 1 to 14 any claim。
16. method according to claim 15, it is characterised in that: in alkylated reaction, being total hydrocarbon feed by iso-butane and C3～C5 olefin, the mol ratio of iso-butane and C3～C5 alkene is 1:1～300:1。
17. method according to claim 16, it is characterised in that: the mol ratio of iso-butane and C3～C5 alkene is 3:1～50:1。
18. method according to claim 15, it is characterised in that: in alkylated reaction, catalyst sulfuric acid is concentrated sulphuric acid, and the sour hydrocarbon volume ratio of the hydrocarbon mixture of concentrated sulphuric acid and iso-butane and C3～C5 alkene is 0.1:1 ~ 5:1, and the mass concentration of concentrated sulphuric acid is 90%～97%。
19. method according to claim 18, it is characterised in that: in alkylated reaction, the sour hydrocarbon volume ratio of the hydrocarbon mixture of concentrated sulphuric acid and iso-butane and C3～C5 alkene is 0.5:1 ~ 1.5:1, and the mass concentration of concentrated sulphuric acid is 93%～96%。
20. method according to claim 15, it is characterised in that: in alkylated reaction, reaction temperature is-20～15 DEG C, and reaction pressure is to maintain the pressure that hydrocarbon mixture is liquid phase at the reaction temperatures。
21. method according to claim 15, it is characterised in that: in alkylated reaction, reaction temperature is-10～10 DEG C, and reaction pressure is 0.2 ~ 1.5MPa。
22. method according to claim 21, it is characterised in that: reaction temperature is-5～5 DEG C, and reaction pressure is 0.3 ~ 0.8MPa。
23. method according to claim 15, it is characterised in that: the rotating speed of alkylation reactor revolving bed is 50～5000 revs/min。
24. method according to claim 23, it is characterised in that: the rotating speed of alkylation reactor revolving bed is 150～2000 revs/min。
25. method according to claim 15, it is characterised in that: reaction mass time of staying in reactor is 2～600 seconds。
26. method according to claim 25, it is characterised in that: reaction mass time of staying in reactor is 10～100 seconds。
27. method according to claim 15, it is characterised in that: in alkylated reaction, adopt circulating cooling gas control reaction temperature, circulating cooling gas employing not with the arbitrary gas of material reaction in response system。
28. method according to claim 27, it is characterised in that: circulating cooling gas is nitrogen, hydrogen, noble gas, carbon monoxide, carbon dioxide, methane or ethane。
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| DE102016100620A1 (en) * | 2015-12-23 | 2017-06-29 | Anton LEDWON | Method for controlling a chemical reaction |
| CN106929093B (en) * | 2015-12-31 | 2019-02-15 | 中国石油天然气股份有限公司 | A kind of alkylation and device of iso-butane and C3~C5 alkene |
| CN108069498A (en) * | 2016-11-11 | 2018-05-25 | 中国石油化工股份有限公司抚顺石油化工研究院 | A kind of new organic wastewater treatment process |
| CN108069501A (en) * | 2016-11-11 | 2018-05-25 | 中国石油化工股份有限公司抚顺石油化工研究院 | A kind of technique for handling organic wastewater |
| CN108264929B (en) * | 2016-12-30 | 2020-05-08 | 中国石油天然气股份有限公司 | Sulfuric acid alkylation method |
| CN111380377A (en) * | 2018-12-31 | 2020-07-07 | 中国石油化工股份有限公司 | Quench tower and sulfur-containing gas purification process |
| CN112745898A (en) * | 2019-10-31 | 2021-05-04 | 中国石油化工股份有限公司 | Alkylation method |
| CN115430379A (en) * | 2021-06-04 | 2022-12-06 | 中国石油天然气股份有限公司 | Alkylation reactor |
| CN113952917B (en) * | 2021-10-18 | 2022-08-26 | 济源市鲁泰纳米材料有限公司 | Hypergravity reactor and preparation method of active nano zinc oxide prepared by same |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5443799A (en) * | 1993-08-03 | 1995-08-22 | Orgral International Technologies Corporation | Process for the alkylation of olefins and apparatus for carrying out this process and others |
| CN2790575Y (en) * | 2005-03-24 | 2006-06-28 | 兰州炼油化工设计院 | Horizontal allkylation reactor |
| CN101104570A (en) * | 2006-06-23 | 2008-01-16 | 催化蒸馏技术公司 | Paraffin alkylation |
| CN103357369A (en) * | 2012-03-29 | 2013-10-23 | 中国石油化工股份有限公司 | Alkylation reaction device and method |
-
2013
- 2013-10-24 CN CN201310503460.1A patent/CN104549114B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5443799A (en) * | 1993-08-03 | 1995-08-22 | Orgral International Technologies Corporation | Process for the alkylation of olefins and apparatus for carrying out this process and others |
| CN2790575Y (en) * | 2005-03-24 | 2006-06-28 | 兰州炼油化工设计院 | Horizontal allkylation reactor |
| CN101104570A (en) * | 2006-06-23 | 2008-01-16 | 催化蒸馏技术公司 | Paraffin alkylation |
| CN103357369A (en) * | 2012-03-29 | 2013-10-23 | 中国石油化工股份有限公司 | Alkylation reaction device and method |
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