CN103242895B - C4 alkylation production method and device - Google Patents
C4 alkylation production method and device Download PDFInfo
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- CN103242895B CN103242895B CN201310140601.8A CN201310140601A CN103242895B CN 103242895 B CN103242895 B CN 103242895B CN 201310140601 A CN201310140601 A CN 201310140601A CN 103242895 B CN103242895 B CN 103242895B
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Abstract
The invention discloses a operation method of a C4 alkylation production device comprises the following steps: sufficiently emulsifying liquid-phase C4 alkane and concentrated sulfuric acid outside the device by utilizing a stirring device and then entering into the device from a tower a phase feeding tube on the tower top via a material pump under the condition that the temperature is preserved to 2-10 DEG C; entering gas-phase C4 alkyl olefin into the device from the tower top and downwards flows along with the liquid phase to pass through a padding section for acid-hydrocarbon layering; adding fresh liquid-phase C4 alkyl olefin between filler sections of a tower reactor by adopting a spray head type feeding tube; passing the gas liquid phase through a self-mixing device between the filler sections, preserving the temperature in the tower to 2-18 DEG C; flowing gas entering from the tower top and gas phase C4 alkyl olefin which is evaporated due to being heated in a reaction process out of a tower-bottom pipeline; and flowing reacted alkyl oil and concentrated sulfuric acid out of the tower-bottom pipeline. According to the C4 alkylation production method and the C4 alkylation production device, the emulsifying degree of acid hydrocarbon in the whole reactor is ensured; reaction heat is taken away by self-evaporation of the liquid-phase C4 olefin in the reaction process, so that the reaction is at a proper temperature, and the investment is saved.
Description
Technical field
The invention belongs to petroleum refining field, relate to a kind of C
4alkylation production method and device.
Background technology
Along with the development of Chinese national economy, the pollution problem of car exhaust gas to air more and more causes concern.The haze weather of nearest Beijing-Tianjin area allows this problem become the focus of people's concern.Its main cause is the sulfur-nitrogen compound that China produces containing high level in gasoline, and the moieties of sulfur-nitrogen compound except deviating from oil, comes from oil blend component (reducing the composition of octane number) more.Therefore, how to produce the clean oil blend component of the environmental protection standard of load country increasingly stringent, become the great problem of petroleum refining industry.
The alkylate oil that iso-butane and small-numerator olefin generate is C
5~ C
9isoparaffin mixture, wherein to be rich in the C of various trimethylpentane
8for main component, it is desirable clean gasoline with high octane component.
Alkylate oil has following characteristics: (1) octane number is high, and in internal combustion engine after burning, exhaust Smoke is few, does not cause pinking, is the desirable high-octane rating blending component of clean gasoline; (2) not containing alkene, aromatic hydrocarbons, sulfur content is also very low, gasoline alkylate is called in gasoline the content of the harmful constituent such as alkene, aromatic hydrocarbons, sulphur that can be reduced by diluting effect in gasoline; (3) vapour pressure is lower; (4) alkylate oil is almost made up of saturated branched alkanes completely, therefore can also be made various solvent naphtha with alkylate oil and use.
Just because of the various advantages of gasoline alkylate, make alkylation process flourish.With the concentrated sulfuric acid be Catalyst Production alkylate oil as production technology main now, also exist in implementation process and select many problems, mainly contain following two aspects: (1) liquid phase C
4alkane alkene is not soluble in concentrated sulfuric acid, very easily layering, and reaction cannot normally be carried out; (2) alkylated reaction is exothermic reaction, and liquid phase C
4alkane olefin alkylation reaction carries out at low temperatures, the carrying out of the accumulation impact reaction of heat, and many side reactions can occur.
Therefore, the technological process finding a kind of high-efficiency and economic becomes an important research topic.
Summary of the invention
The invention reside in that to propose a kind of take liquid sulfuric acid as the novel C of catalyst
4alkylating production technology and corresponding reactor, comparatively other techniques, the present invention can make sulfuric acid and C
4alkane alkene is better mixed, and alkylated reaction can be carried out more fully.Because alkylated reaction is exothermic reaction, the present invention utilizes the evaporation of alkane alkene to take away heat of reaction, is react to carry out under optimum conditions, has saved the expense of refrigerating plant simultaneously.
The technology of the present invention is as follows:
A kind of C
4alkylation production method take the concentrated sulfuric acid as catalyst, under the condition of the pressure of 400-500KPa and 2-18 DEG C, realize C
4alkene and C
4the alkylated reaction of alkane; Alkane alkene is than being 2:1 ~ 16:1, and acid hydrocarbon ratio is 1:1 ~ 4:1.
A kind of C of the present invention
4alkylation process units, adopts tower-type reaction device, and in tower, segmentation loads filler, and tower top arranges gas-phase feed pipe 2, liquid phase feeding pipe 1 respectively, arranges liquid phase feeding pipe 4, arrange C at the bottom of tower between packing section
4alkane alkene gaseous phase outlet 6, liquid-phase outlet pipe 7; Be arranged between packing section from mixing arrangement 5 in tower, fluid is at the undulating flow of mixing arrangement in transverse direction.
Described every section of packing section height is 0.2m ~ 2m, and in tower, hop count is 2 ~ 10 sections.
Described liquid phase feeding pipe, adopts arborizations 8 structure, main pipeline is opened some small pipelines, small pipeline is opened uniform aperture 9, adopts spray nozzle type feed pipe.
C of the present invention
4the method of operating of alkylation process units, liquid phase C
4alkane and 98% concentrated sulfuric acid utilize agitating device fully emulsified outside device, keep temperature be 2-10 DEG C through feedstock pump from tower top liquid phase feed pipe 1 access to plant; Temperature is 2-10 DEG C, the 500-600KPa gas phase C that pressure is
4alkane alkene, from top gaseous phase feed pipe 2 access to plant, flows downward with liquid phase, through the sour hydrocarbon layering of filler 3 sections; Spray nozzle type feed pipe 4 is adopted to add fresh liquid phase C between tower reactor packing section
4alkane alkene, temperature is 2-10 DEG C; Liquid phase between packing section from mixing arrangement 5, keep temperature 2-18 DEG C in tower; The gases at high pressure that tower top enters and the gas phase C that course of reaction evaporates by heat out
4alkane alkene flows out from tower bottom pipeline 6, and reacted alkylate oil and the concentrated sulfuric acid flow out from tower bottom pipeline 7.
The invention has the advantages that: to utilize in tower sprayed feed and from mixing arrangement, ensure that the emulsification degree of sour hydrocarbon in whole reactor, ensure that reaction is carried out smoothly; Utilize liquid phase C simultaneously
4heat of reaction is taken away in the spontaneous evaporation of alkane alkene in course of reaction, makes reaction be in suitable temperature, and has saved the investment of heat-exchanger rig.
Accompanying drawing explanation
Fig. 1-alkylation tower reactor;
Fig. 2-spray nozzle type feed pipe;
Wherein: 1-liquid phase C
4alkane and concentrated sulfuric acid mixture feed pipe; 2-C
4alkane alkene gas-phase feed pipe; 3-filler;
Liquid phase C between 4-packing section
4alkane olefin feedstocks pipe; 5-is from blender; 6-C
4alkane alkene gaseous phase outlet; 7-alkylate oil and sulfuric acid export; 8-branch; 9-perforate.
Detailed description of the invention
Be described below in conjunction with accompanying drawing:
Take the concentrated sulfuric acid as catalyst, under the condition of the pressure of 400-500KPa and 2-18 DEG C, realize C
4alkene and C
4the alkylated reaction of alkane; Alkane alkene is than being 2:1 ~ 16:1, and acid hydrocarbon ratio is 1:1 ~ 4:1.
C
4alkylation process units, adopts tower-type reaction device, spontaneous evaporation heat-obtaining technology and Ta Nei from mixing arrangement.The main device of reaction is tower reactor, and in tower, segmentation loads filler 3, and every section of packing section height is 0.2m ~ 2m, and in tower, hop count is 2 ~ 10 sections.Tower top arranges gas-phase feed pipe 2, liquid phase feeding pipe 1 respectively, arranges liquid phase feeding pipe 4, arrange C at the bottom of tower between packing section
4alkane alkene gaseous phase outlet 6, liquid-phase outlet pipe 7; All liquid phase feeding pipes, all adopt spray nozzle type feed pipe, it adopts arborizations 8 structure, and main pipeline is opened some small pipelines, small pipeline is opened uniform aperture 9, installation high-voltage nozzle.Is arranged between packing section from mixing arrangement 5 in tower, fluid in horizontal undulating flow, reaches the object making liquid phase emulsification again at this mixing arrangement.
Material reaction flow process of the present invention is as follows: liquid phase C
4alkane and 98% concentrated sulfuric acid utilize agitating device fully emulsified outside device, keep temperature be 2-10 DEG C through feedstock pump from tower top liquid phase feed pipe 1 access to plant; Temperature is 2-10 DEG C, and pressure is 500-600KPa gas phase C
4alkane alkene, from top gaseous phase feed pipe 2 access to plant, flows downward with liquid phase, alleviates sour hydrocarbon layering through filler 3 sections; Spray nozzle type feed pipe 4 is adopted to add fresh liquid phase C between tower reactor packing section
4alkane alkene, temperature is 2-10 DEG C, evenly sprays into liquid phase mixture, makes it fully emulsified; Liquid phase between packing section when mixing arrangement 5, in gas phase disturbance with under the effect of mixing arrangement, realize emulsification again; When liquid phase flows downward, alkylated reaction occurs, the heat that reaction produces makes alkane, alkene evaporate, and heat of reaction is taken away by the heat of vaporization needed for evaporation, keeps temperature 2-18 DEG C in tower; The gases at high pressure that tower top enters and the gas phase C that course of reaction evaporates by heat out
4alkane alkene flows out from tower bottom pipeline 6, and reacted alkylate oil and the concentrated sulfuric acid flow out from tower bottom pipeline 7.
From mixing arrangement 5 in tower, to be arranged between packing section fluid at this mixing arrangement in horizontal undulating flow, in gas phase disturbance with under the effect of mixing arrangement, to reach the object making liquid phase emulsification again.
Spray nozzle type feed pipe 4 is adopted to add fresh liquid phase C between tower reactor filler 3 sections
4alkane alkene, evenly sprays into liquid phase mixture, makes it fully emulsified.
, there is alkylated reaction when liquid phase flows downward in described alkylation production method, the heat that reaction produces makes alkane, alkene evaporate, and heat of reaction is taken away by the heat of vaporization needed for evaporation, keeps temperature constant in tower.
Typical example:
For alkylate oil output 8t/h, this technique is described:
Core reaction device tower height 2.5m, diameter 1m.
In tower reactor, segmentation loads filler 3, and packing section is divided into 3 layers, and every section of packed height is 0.5m.
Liquid phase C
4alkane and 98% concentrated sulfuric acid utilize agitating device fully emulsified outside device, and temperature controls at about 4 DEG C, and alkane alkene is than being 8:1, and acid hydrocarbon ratio is 1:0.5, and through feedstock pump from tower top feed pipe 1 high speed access to plant, inlet amount is 15t/h.
High pressure vapor C
4alkane alkene enters from top gaseous phase feed pipe 2, enters filler 3 with the downward flow at high speed of liquid phase.
Spray nozzle type feed pipe 4 is adopted to add fresh liquid phase C between filler 3 sections
4alkane alkene, inlet amount is 1.6t/h, and temperature about 4 DEG C, evenly sprays into liquid phase mixture, makes it fully emulsified.
The gases at high pressure that tower top enters and the gas phase C that course of reaction evaporates by heat out
4alkane alkene flows out from tower bottom pipeline 6, and reacted alkylate oil and the concentrated sulfuric acid flow out from tower bottom pipeline 7, and the gas phase evaporated takes away the heat that reaction produces, and maintains temperature constant in tower.
Adopt C of the present invention
4alkylation reaction technique, the yield of alkylate oil is 97%, and comparatively other process recovery ratio improves 5%; Owing to adopting novel Self-evaporating type heat-obtaining mode, save refrigerating plant investment 10%.
Claims (3)
1. a C
4alkylation process units, it is characterized in that adopting tower-type reaction device, be that catalyst carries out alkylated reaction with the concentrated sulfuric acid, under the condition of the pressure of 400-500KPa and 2-18 DEG C, in tower, segmentation loads filler, tower top arranges gas-phase feed pipe (2), liquid phase feeding pipe (1) respectively, liquid phase feeding pipe (4) is set between packing section, adopt arborizations (8) structure, main pipeline is opened some small pipelines, small pipeline is opened uniform aperture (9), adopts spray nozzle type feed pipe; At the bottom of tower, C is set
4alkane alkene gaseous phase outlet (6), liquid-phase outlet pipe (7); Be arranged between packing section from mixing arrangement (5) in tower, fluid is at the undulating flow of mixing arrangement in transverse direction.
2. device as claimed in claim 1, it is characterized in that every section of packing section height is 0.2m-2m, in tower, hop count is 2-10 section.
3. the method for operating of the device of claim 1, is characterized in that liquid phase C
4alkane and 98% concentrated sulfuric acid utilize agitating device fully emulsified outside device, keep temperature be 2-10 DEG C through feedstock pump from tower top liquid phase feed pipe (1) access to plant; Temperature is 2-10 DEG C, and pressure is 500-600KPa gas phase C
4alkane alkene, from top gaseous phase feed pipe (2) access to plant, flows downward with liquid phase, through the layering of filler (3) section acid hydrocarbon; Spray nozzle type feed pipe (4) is adopted to add fresh liquid phase C between tower reactor packing section
4alkane alkene, temperature is 2-10 DEG C; Liquid phase between packing section from mixing arrangement (5), keep temperature 2-18 DEG C in tower; The gases at high pressure that tower top enters and the gas phase C that course of reaction evaporates by heat out
4alkane alkene flows out from tower bottom pipeline (6), and reacted alkylate oil and the concentrated sulfuric acid flow out from tower bottom pipeline (7).
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| CN201310140601.8A CN103242895B (en) | 2013-04-22 | 2013-04-22 | C4 alkylation production method and device |
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|---|---|---|---|
| CN201310140601.8A CN103242895B (en) | 2013-04-22 | 2013-04-22 | C4 alkylation production method and device |
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| CN105016946B (en) * | 2014-04-29 | 2017-09-29 | 中国石油化工股份有限公司 | A kind of alkylation reaction method and device of the acid catalyzed isoparaffin of liquid and alkene |
| CN105268394B (en) * | 2014-07-17 | 2020-06-16 | 中国石油化工股份有限公司 | Liquid acid alkylation reactor and application method thereof |
| CN105219428B (en) * | 2015-11-03 | 2017-10-27 | 中石化炼化工程（集团）股份有限公司 | A kind of method of sulfuric acid alkylation reaction |
| EP3676236A1 (en) * | 2017-08-28 | 2020-07-08 | SABIC Global Technologies B.V. | Systems and methods for converting n-butane to iso-butane |
| CN109293512A (en) * | 2018-12-10 | 2019-02-01 | 杭州若水化学科技有限公司 | Esters of acrylic acid product production device |
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| DE102007059243A1 (en) * | 2007-12-07 | 2009-06-10 | Uhde Gmbh | Process for the desulfurization of olefin-containing starting materials |
| US20090171133A1 (en) * | 2007-12-28 | 2009-07-02 | Chevron U.S.A. Inc. | Ionic liquid catalyst alkylation using a loop reactor |
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