CN104276916B - A kind of system and separation method preparing Trimethylmethane - Google Patents
A kind of system and separation method preparing Trimethylmethane Download PDFInfo
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- CN104276916B CN104276916B CN201310286430.XA CN201310286430A CN104276916B CN 104276916 B CN104276916 B CN 104276916B CN 201310286430 A CN201310286430 A CN 201310286430A CN 104276916 B CN104276916 B CN 104276916B
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Abstract
The invention discloses a kind of system and the separation method of preparing Trimethylmethane.Described system comprises: extractive distillation column, alkane water wash column, stripping tower, alkene water wash column, solvent recovery tower, hydrogenator, hydrogenation input and output material interchanger, hydrogenation feed heater, hydrogenation tripping device, lightness-removing column, Trimethylmethane finishing column.Hydrogenation tripping device comprises: hydrogenation aftercooler, heat from hydrogenation separating tank and add hydrogen-cooled separating tank; Or comprise hydrogenation aftercooler and hydrogenation separating tank.Method comprises: after ether, carbon four can obtain butylene product through extracting rectifying; Reclaim the high pressure exhaust gas after hydrogenation reaction, improve the rate of recovery of Trimethylmethane product; Unsaturated with saturated carbon four raw material after extracting rectifying and hydrogenation obtained Trimethylmethane product.The present invention can process carbon four after all refinery Cs four and ethylene unit ether, by solvent waste heat recovery, improves the economic benefit of device.
Description
Technical field
The present invention relates to carbon four field, furtherly, relate to a kind of system and the separation method of preparing Trimethylmethane.
Background technology
Many refining & chemical industry integration enterprises of China lighter hydrocarbons aboundresources, C-4-fraction is superfluous.Along with the rapid raising of crude oil in China working ability and the continuous increase of ethylene yield, as carbon four resource of petrochemical by-product also in continuous expansion.How fully, reasonably utilize the C-4-fraction of refinery gas and ethylene unit by-product, excavate the potential value of carbon four-product, become one of problem that people pay close attention to.Contain in C-4-fraction 1,3-divinyl can be separated by the method for extracting rectifying and be used as to produce synthetic rubber, iso-butylene in C-4-fraction is reacted by ether-based device and methyl alcohol and generates MTBE and obtain highly purified 1-butylene by further precision fractional distillation, and the utilization of other carbon Four composition is also less.Divinyl is produced in the raw material that in carbon Four composition, 1-butylene, 2-butylene can be produced as methylethylketone or oxydehydrogenation.Normal butane can be used as the raw material producing cis-butenedioic anhydride, and Trimethylmethane can be produced aviation fuel, can make refrigeration agent, and isopropylcarbinol, propylene oxide etc.In recent years because the demands such as methylethylketone, cis-butenedioic anhydride, isopropylcarbinol and propylene oxide increase year by year, make the technique that butane is separated with butylene, more and more cause the attention of people.
Refinery C four wide material sources, are mainly divided into two types, and a kind of is the saturated carbon four containing alkene≤5%wt, the unsaturated carbon four of another kind of olefin(e) centent 40 ~ 50%wt, carbon four mainly alkane and monoolefine after ethylene unit ether, olefin(e) centent 30 ~ 60%wt.Current, these C 4 mixture overwhelming majority are burnt as liquefied gas as fuel, and chemical utilization rate is lower, and due to butane, the good prospects for commercial application of alkene, its extraction and application is just most important.
Each component boiling point and relative volatility in table 1 C-4-fraction
C-4-fraction is close by more than 10 kinds of boiling points, easily form the component composition of azeotrope to each other, as shown in table 1, therefrom isolate purity meet the alkane of application requiring and alkene difficulty higher, one is that relative volatility between iso-butylene and 1-butylene is only 1.005, atmospheric boiling point only differs from 0.64 DEG C, is difficult to be separated by the method for conventional distillation, and the catalytic distillation technology that adopts makes iso-butylene and methyl alcohol Reactive Synthesis MTBE thus removes iso-butylene more at present; Two is that the relative volatility of normal butane and Trans-2-butene in the C_4 hydrocarbon after etherificate is also less, and the developability of normal butane is between 1-butylene and Trans-2-butene, needs considerable number of theoretical plate by the method for conventional distillation, and technique is comparatively complicated.Generally extraction fractional distillation is adopted in prior art.Conventional selective solvent has dimethyl formamide (DMF), acetonitrile (ACN), N-Methyl pyrrolidone (NMP) and N-N-formyl morpholine N-(NFM) etc., as Nippon Zeon Co., Ltd. patent JP6-92876, IFP patent EP0501848A1 adopt the technology of DMF extraction agent three-column process flow separation of extractive distillation butane and butylene, shortcoming be need use gas compressor, investment and energy consumption larger; KrupUhde company of Germany is based on the rich experiences of aromatic hydrocarbon extracting rectifying, develop morpholine solvent technique, this technique adopts the extraction and distillation technology of two-tower process separating butane and butylene, and dropped into suitability for industrialized production first in 1998, the advantage of this technique eliminates compressor, shortcoming is that the boiling point of solvent is too high, and energy consumption is larger.
Chinese patent CN1358697A discloses the method with methylethylketone series mixed solvent separating butane and butylene, and Chinese patent CN1681754A discloses the method as separated from solvent butane and butylene such as employing polar solvent dimethyl formamide, N-Methyl pyrrolidone, acetonitrile; Chinese patent CN101417913A discloses and adopts the multiple mixed solvent separating butane of ionic liquid, salt, methylethylketone and N-N-formyl morpholine N-and the method for butylene.Its essence of these methods is all adopt different solvents, by improving butane and the relative degree of waving of butylene, reaches the object of separation.But shortcoming is only applicable to the higher C 4 mixture of olefin(e) centent, and as olefin(e) centent is lower, then economic benefit is low, and mostly do not relate to the optimization of heat exchanger network, energy-saving effect is not good.
Chinese patent CN102294203A discloses carbon four secondary hydrogenation device in a kind of catalytic pyrolysis ethene and technique, by adopting two sections of selective hydrogenations, avoid 1,3-divinyl deep hydrogenation induce reaction device coking, reduce the problem in catalyzer work-ing life and plant running cycle, directly directly can carry out hydrogenation to mixed c 4, improve the utilization ratio of raw material.But concrete separation method is not related to for C 4 mixture that is a small amount of containing diolefine or that do not have, does not relate to the removal methods of the impurity such as organosulfur nitrogen yet.
Chinese patent CN102188985A discloses a kind of C-4-fraction selective hydrogenation catalyst and preparation method thereof, this catalyzer can alkynes selective hydrogenation in C-4-fraction, divinyl substantially not contained by, catalyzer has high reactivity, highly selective and preparation method are simple, is widely used.But this invention is mainly to the selective hydrogenation of alkynes in C-4-fraction, there is no the method for hydrotreating of monoolefine in alkane, alkene mixture, and be the preparation of catalyzer, do not relate to separation method, do not relate to the removal methods of the impurity such as organosulfur nitrogen yet.
Chinese patent CN102146009A discloses a kind of method of hydrotreating of unsaturated carbon four, and the method is reacted by two-stage hydrogenation after utilizing unsaturated carbon four to mix with hydrogen, and gained reaction product obtains saturated carbon four-product after cooling, separation.But this invention mainly relates to the reaction of unsaturated carbon four cut fraction hydrogenation generates the method for saturated carbon four, does not relate to the removal methods of the impurity such as organosulfur nitrogen, do not relate to yet and how to be separated normal butane in saturated carbon Four composition and Trimethylmethane.
Summary of the invention
Cannot unify for carbon four after refinery C 4 mixture and ethylene unit ether the problem processing obtained highly purified Trimethylmethane for solving prior art, the invention provides a kind of system and the separation method of preparing Trimethylmethane.By extracting rectifying and hydrogenation technique are carried out reasonable combination, the present invention can process carbon four after all refinery Cs four and ethylene unit ether in principle, and meanwhile, extracting system is by adopting heat exchange network optimization technology, by solvent waste heat recovery, improve the economic benefit of device.
An object of the present invention is to provide a kind of system preparing Trimethylmethane.
Comprise: extractive distillation column, alkane water wash column, stripping tower, alkene water wash column, solvent recovery tower, hydrogenator, hydrogenation input and output material interchanger, hydrogenation feed heater, hydrogenation tripping device, lightness-removing column, Trimethylmethane finishing column;
Described extracting rectifying top of tower connects alkane water wash column, and extracting rectifying tower bottom connects stripping tower; Stripper top connects alkene water wash column, is connected bottom stripping tower with extractive distillation column top;
Described alkane water wash column top connects hydrogenation input and output material interchanger; Described hydrogenation input and output material heat exchanger exit connects hydrogenator top after connecting hydrogenation feed heater;
Described alkane water wash column is connected solvent recovery tower with bottom alkene water wash column; Solvent recuperation top of tower connects solvent recovery tower condenser after connecting Trimethylmethane finishing column intermediate reboiler again, and solvent recovery tower condensator outlet pipeline is divided into two-way: a road returns to solvent recovery tower top, and another road connects extractive distillation column top;
Hydrogenation tripping device is connected after connecting hydrogenation input and output material interchanger bottom described hydrogenator, hydrogenation separation unit overhead outlet line is divided into two-way, is connected hydrogenation input and output material interchanger after merging after a road connects compressor suction tank, compressor successively with alkane water wash column top exit pipeline; Another road connects lightness-removing column;
Hydrogenation separation unit bottoms connects lightness-removing column; Trimethylmethane finishing column is connected bottom lightness-removing column.
Described hydrogenation tripping device is in order to separating hydrogen gas and hydro carbons, and hydrogenation tripping device can adopt one of following two kinds of compositions:
A) hydrogenation tripping device comprises heat from hydrogenation separating tank, hydrogenation aftercooler and adds hydrogen-cooled separating tank;
Heat from hydrogenation separating tank is connected after connecting hydrogenation input and output material interchanger bottom described hydrogenator, heat from hydrogenation separating tank top connects hydrogenation aftercooler successively and adds hydrogen-cooled separating tank, add hydrogen-cooled separating tank top exit pipeline and be divided into two-way, one tunnel connects compressor suction tank, another road connects lightness-removing column top, connects lightness-removing column bottom heat from hydrogenation separating tank.
B) hydrogenation tripping device comprises: hydrogenation aftercooler and hydrogenation separating tank;
Hydrogenation aftercooler and hydrogenation separating tank is connected successively after connecting hydrogenation input and output material interchanger bottom described hydrogenator, hydrogenation separating tank top exit pipeline is divided into two-way, one tunnel connects compressor suction tank, and another road connects lightness-removing column top, connects lightness-removing column bottom hydrogenation separating tank.
Described reaction discharging can have two kinds of modes after the heat exchange of hydrogenation input and output material interchanger, one carries out gas-liquid separation for being introduced into heat from hydrogenation separating tank, top gas phase enters the cold separating tank of hydrogenation after the cooling of hydrogenation aftercooler, add the isolated hydrogen part in hydrogen-cooled separating tank top and introduce lightness-removing column top as high pressure exhaust gas, another part enters compressor suction tank, and heat from hydrogenation separating tank bottom liquid phases connects lightness-removing column; Another kind of mode for first entering hydrogenation separating tank through gas-liquid separation after the cooling of hydrogenation aftercooler, hydrogenation separating tank top portion from hydrogen a part as high pressure exhaust gas introduce lightness-removing column top, another part enters compressor suction tank, and hydrogenation separating tank bottom liquid phases connects lightness-removing column.
Preferred employing first kind of way.
Described extractive distillation column bottom is respectively arranged with extraction Steam reboiler, extraction solvent reboiler and extraction intermediate reboiler; Extracting rectifying top of tower is provided with evaporator overhead condenser;
Be connected with extractive distillation column top after connecting extraction solvent reboiler, extraction intermediate reboiler, feed preheater, solvent cooler bottom stripping tower successively.
The above hydrogenation feed heater can adopt common heating installation in prior art, as: electrically heated, steam heating or process furnace etc.
Specifically can by the following technical solutions:
Described extracting rectifying top of tower connects alkane water wash column, and extracting rectifying tower bottom connects stripping tower;
Described stripper top connects alkene water wash column, with extractive distillation column top is connected after connecting extraction solvent reboiler, extraction intermediate reboiler, raw materials evaporate tank preheater, solvent cooler successively bottom stripping tower.
Described alkane water wash column top connects hydrogenation input and output material interchanger;
Described alkane water wash column is connected solvent recovery tower with bottom alkene water wash column; Solvent recuperation top of tower connects solvent recovery tower condenser after connecting Trimethylmethane finishing column intermediate reboiler again, and solvent recovery tower condensator outlet pipeline is divided into two-way: a road returns to solvent recovery tower top, and another road connects extractive distillation column top;
Described hydrogenation input and output material interchanger is connected with hydrogenator top after connecting hydrogenation feed heater;
Described compressor suction tank connects compressor and hydrogenation input and output material interchanger;
Described hydrogenator bottom is connected with hydrogenation input and output material interchanger, heat from hydrogenation separating tank successively; Heat from hydrogenation separating tank top with add hydrogen-cooled separating tank and be connected, add hydrogen-cooled separating tank top exit pipeline and be divided into two-way, a road connects compressor suction tank, and another road connects lightness-removing column top, connects lightness-removing column bottom heat from hydrogenation separating tank;
Be connected with Trimethylmethane finishing column bottom described lightness-removing column; Described Trimethylmethane finishing column top connects Trimethylmethane product line.
Two of object of the present invention is to provide a kind of separation method preparing Trimethylmethane.
Comprise:
After ether, carbon four can obtain butylene product through extracting rectifying;
Unsaturated carbon four raw material is through extracting rectifying, hydrogenation obtained Trimethylmethane product after being separated; Saturated carbon four raw material obtains Trimethylmethane product after hydrogenation is separated.
Specifically comprise the following steps:
A () unsaturated carbon four enters extractive distillation column after gasifying and carries out extracting rectifying, the butane that tower top obtains enters hydrogenation input and output material interchanger after alkane water wash column desolvation;
B () enters stripping tower by the mixture of extracting rectifying tower bottom extraction C 4 olefin and solvent, the C 4 olefin that tower top obtains obtains carbon four monoolefine product again after alkene water wash column desolvation;
(c) by the saturated carbon four out-of-bounds come with to be mixed by alkane water wash column top extraction C 4 materials after enter hydrogenation input and output material interchanger, hydrogenation feed heater successively after, enter hydrogenator by a small amount of monoolefine and diolefin hydrotreated lube base oil and remove micro-organosulfur nitrogen impurity;
D () is connected with extractive distillation column top as thermal source successively by the circulating solvent of stripping tower reactor extraction after extraction solvent reboiler, extraction intermediate reboiler, feed preheater heat exchange after solvent cooler is cooled to 40 ~ 60 DEG C; Circulating solvent is extracted a small gangs of material out and is sent to solvent recovery tower simultaneously;
E () to be merged together with the shallow bid material that circulating solvent is extracted out by the solvent of extraction bottom alkane water wash column, alkene water wash column and the mixture of water send to solvent recovery tower after the heat exchange of solvent recovery tower input and output material interchanger;
(f) by solvent recovery tower top gas phase material through with the heat exchange of Trimethylmethane finishing column intermediate reboiler after be cooled to 40 ~ 75 DEG C by solvent recovery tower condenser after point two-way, one tunnel returns solvent recuperation top of tower as backflow, and extractive distillation column top is sent to as solvent in another road;
G () hydrogenator bottom discharge enters hydrogenation tripping device after the heat exchange of hydrogenation input and output material interchanger, an isolated hydrogen part sends into the butane contained by the recovery of lightness-removing column top as high pressure exhaust gas, another part returns to hydrogenator top as recycle hydrogen, and hydrogenation separation unit bottoms material enters lightness-removing column;
H () lightness-removing column bottoms material enters Trimethylmethane finishing column; Trimethylmethane product is obtained by Trimethylmethane finishing column top by rectifying separation.
In step (c), mixed c 4 material enters hydrogenator after being heated to 160 ~ 400 DEG C.
In step (g), when hydrogenation tripping device comprises heat from hydrogenation separating tank, hydrogenation aftercooler and adds hydrogen-cooled separating tank, hydrogenator bottom discharge enters heat from hydrogenation separating tank after input and output material heat exchange is cooled to 50 ~ 100 DEG C, heat from hydrogenation separating tank top gas phase enters the cold separating tank of hydrogenation after hydrogenation aftercooler is cooled to 35 ~ 45 DEG C, add the isolated hydrogen part in hydrogen-cooled separating tank top and introduce lightness-removing column top as high pressure exhaust gas, another part enters compressor suction tank, and heat from hydrogenation separating tank bottom liquid phases enters lightness-removing column;
When hydrogenation tripping device comprises hydrogenation aftercooler and hydrogenation separating tank, hydrogenator bottoms material is after input and output material heat exchange, hydrogenation separating tank is entered again after hydrogenation aftercooler is cooled to 35 ~ 45 DEG C, hydrogenation separating tank top portion from hydrogen a part as high pressure exhaust gas introduce lightness-removing column top, another part enters compressor suction tank, and hydrogenation separating tank bottom liquid phases enters lightness-removing column.
Can by the following technical solutions:
A () unsaturated carbon four enters extractive distillation column after being gasified totally, carry out extracting rectifying by adding solvent, the butane that tower top obtains enters hydrogenation input and output material interchanger after alkane water wash column desolvation;
B () enters stripping tower by the mixture of extracting rectifying tower bottom extraction C 4 olefin and solvent, the C 4 olefin that stripping tower top obtains obtains carbon four monoolefine product again after alkene water wash column desolvation;
(c) by the circulating solvent of extraction bottom stripping tower through extraction solvent reboiler, extraction intermediate reboiler, after the heat exchange of raw materials evaporate tank preheater, be cooled to 40 ~ 60 DEG C finally by solvent cooler and return extracting rectifying top of tower as solvent feed; Circulating solvent is extracted a small gangs of out and is sent to solvent recovery tower simultaneously;
D () to be merged together with the shallow bid material that circulating solvent is extracted out by the solvent of extraction bottom alkane water wash column, alkene water wash column and the mixture of water send to solvent recovery tower after solvent recovery tower input and output material interchanger is heated to 60 ~ 100 DEG C;
(e) by solvent recovery tower top gas phase material through with the heat exchange of Trimethylmethane finishing column intermediate reboiler after be cooled to 40 ~ 75 DEG C by solvent recovery tower condenser after point two-way, one tunnel returns solvent recuperation top of tower as backflow, and extractive distillation column top is sent to as solvent in another road;
F () is by the saturated carbon four out-of-bounds come and be mixed into hydrogenation input and output material interchanger by alkane water wash column top extraction material, be warming up to 160 ~ 400 DEG C through hydrogenation feed heater again after being preheated to 140 ~ 250 DEG C by hydrogenation input and output material interchanger, finally enter hydrogenator by a small amount of monoolefine and diolefin hydrotreated lube base oil and be H micro-organosulfur nitrogen transformation
2s and NH
3;
(g) hydrogenator bottom discharge through with hydrogenation charging heat exchange after be cooled to 50 ~ 100 DEG C after can have two kinds of modes, one first enters hydrogenation separating tank through gas-liquid separation after hydrogenation aftercooler is cooled to 35 ~ 45 DEG C, hydrogenation separating tank top gas phase connects compressor suction tank, and hydrogenation separating tank bottom liquid phases connects lightness-removing column; Another kind of mode carries out gas-liquid separation for being introduced into heat from hydrogenation separating tank, top gas phase enters the cold separating tank of hydrogenation after hydrogenation aftercooler is cooled to 35 ~ 45 DEG C, add hydrogen-cooled separating tank top and connect compressor suction tank, add hydrogen-cooled separation tank bottom portion and connect heat from hydrogenation separating tank, heat from hydrogenation separating tank bottom liquid phases connects lightness-removing column.
Hydrogenation separating tank or add hydrogen-cooled separating tank top gas phase major part and return hydrogenation reaction charging as circulating hydrogen, another part as high pressure exhaust gas send into lightness-removing column top reclaim contained by butane, to maintain in recycle hydrogen system hydrogen content with this and stablize.
H () fresh hydrogen enters compressor suction tank from out-of-bounds merging with cold separating tank top gas body, then after compressor supercharging, enter hydrogenation input and output material interchanger together with C 4 mixture;
(i) enter lightness-removing column, by rectifying separation removed overhead H by heat from hydrogenation separating tank bottoms material
2s, NH
3with carbon one, carbon two, the third-class light constituent of carbon, bottoms material enters Trimethylmethane finishing column; Trimethylmethane product is obtained by Trimethylmethane finishing column top by rectifying separation.
Catalyzer that the present invention adopts is nickel system or palladium series hydrocatalyst.
The processing condition of each equipment of the present invention can adopt the processing condition usually adopted in prior art, in the present invention, can preferably adopt following processing condition:
Hydrogenator is fixed-bed reactor, and reactor inlet temperature is 160 ~ 400 DEG C, and pressure is 1.5 ~ 4.5MpaG, and reaction temperature rising is 2 ~ 50 DEG C, and hydrogen-oil ratio is 0.2 ~ 5 (mol ratio), and liquid volume air speed is 0.5 ~ 6h
-1;
Extractive distillation column working pressure: 0.1 ~ 1MPaG, tower top service temperature: 40 ~ 60 DEG C, stage number 100 ~ 200, reflux ratio 1 ~ 10, solvent ratio 5 ~ 10;
Stripping tower working pressure: 0.1 ~ 1MPaG, tower top service temperature: 40 ~ 60 DEG C, stage number 30 ~ 80, reflux ratio 1 ~ 10;
Alkane water wash column working pressure: 0.1 ~ 1MPaG, tower top service temperature: 35 ~ 50 DEG C, stage number 30 ~ 90, column internals is sieve plate or filler;
Alkene water wash column working pressure: 0.1 ~ 1MPaG, tower top service temperature: 35 ~ 50 DEG C, stage number 30 ~ 90, column internals is sieve plate or filler;
Solvent recovery tower working pressure: 0.005 ~ 0.1MPaG, tower top service temperature: 60 ~ 120 DEG C, stage number 20 ~ 80, reflux ratio 1 ~ 10;
Lightness-removing column working pressure: 1 ~ 3MPaG, tower top service temperature: 20 ~ 100 DEG C, stage number 60 ~ 150, reflux ratio 5 ~ 20;
Trimethylmethane finishing column working pressure: 0.1 ~ 1MPaG, tower top service temperature: 20 ~ 60 DEG C, stage number 80 ~ 150, reflux ratio 1 ~ 10.
Feature of the present invention is:
1) mixed solvent separating butane and the butylene of acetonitrile and water is adopted;
2) extractive distillation column and stripping tower operate all under elevated pressure, tower top temperature about 45 DEG C;
3) solvent is good to carbon four solvability, substantially without Two Liquid Phases in tower;
4) solvent viscosity is little, substantially without foamed phenomenon in tower;
5) by hydrogenation, unsaturated olefin being all converted into saturation of olefins, is H by impurity conversion such as organosulfur nitrogen in raw material
2s and NH
3remove, avoid the impact on product;
6) by rationally arranging heat exchange order, recovered energy to the full extent, reducing system energy consumption, improve the economic benefit of device, reclaim heat by circulating solvent heat exchange and solvent recovery tower, save energy consumption more than 15%;
7) pass through preferably separation process and at utmost reduce the contained rate of Trimethylmethane, make extractive distillation column, lightness-removing column and Trimethylmethane finishing column bottom temperature all lower than 130 DEG C by suitable operating parameters simultaneously, tower top temperature about 45 DEG C, adopt more cheap low-pressure steam and recirculated cooling water to get final product heat exchange, get involved high-grade steam and the refrigerated water of high-quality without the need to outside;
8) the present invention by extracting rectifying and hydrogenation technique are carried out in order, reasonable combination, carbon four after all refinery Cs four and ethylene unit ether can be processed in principle.
9) hydrogen of the separation after a hydrogenation reaction part is introduced lightness-removing column as high pressure exhaust gas by the present invention, can reclaim the Trimethylmethane product carried secretly in high pressure exhaust gas, reduce Trimethylmethane product loss, make Trimethylmethane product yield > 99.7%.
Accompanying drawing explanation
Fig. 1 system schematic (when hydrogenation tripping device comprises heat from hydrogenation separating tank, hydrogenation aftercooler and adds hydrogen-cooled separating tank) preparing Trimethylmethane of the present invention
Fig. 2 system schematic (when hydrogenation tripping device comprises hydrogenation aftercooler and hydrogenation separating tank) preparing Trimethylmethane of the present invention
Description of reference numerals:
1-feed preheater; 2-extractive distillation column; 3-extractive distillation column condenser; 4-extracts Steam reboiler; 5-extraction solvent reboiler; 6-extracts intermediate reboiler; 7-solvent cooler; 8-alkane water wash column; 9-stripping tower; 10-stripper condenser; 11-stripper reboiler; 12-alkene water wash column; 13-solvent recovery tower input and output material interchanger; 14-solvent recovery tower; 15-solvent recovery tower condenser; 16-solvent recovery tower reboiler; 17-hydrogenator; 18-hydrogenation input and output material interchanger; 19-hydrogenation feed heater; 20-heat from hydrogenation separating tank; 21-hydrogenation aftercooler; 23-adds hydrogen-cooled separating tank; 24-compressor suction tank; 25-compressor; 26-hydrogenation separating tank; 29-lightness-removing column; 30-condenser of light component removal column; 31-lightness-removing column reboiler; 32-Trimethylmethane finishing column; 33-Trimethylmethane finishing column intermediate reboiler; 34-Trimethylmethane finishing column condenser; 35-Trimethylmethane finishing column Steam reboiler; Carbon four after 36-ether; 37-supplementing solvent; 38-saturated carbon four; 39-hydrogen make-up; 40-high pressure exhaust gas; 41-butylene; 42-Trimethylmethane product; 43-normal butane; 44-carbon three light constituent
Embodiment
Below in conjunction with embodiment, further illustrate the present invention.
Embodiment:
As shown in Figure 1, a kind of system preparing Trimethylmethane.
Comprise: extractive distillation column 2, alkane water wash column 8, stripping tower 9, alkene water wash column 12, solvent recovery tower 14, hydrogenator 17, hydrogenation input and output material interchanger 18, hydrogenation feed heater 19, heat from hydrogenation separating tank 20, hydrogenation aftercooler 21, add hydrogen-cooled separating tank 23, compressor suction tank 24, compressor 25, lightness-removing column 29, Trimethylmethane finishing column 32;
Described extractive distillation column 2 top connects alkane water wash column 8, connects stripping tower 9 bottom extractive distillation column 2; Stripping tower 9 top connects alkene water wash column 12, is connected bottom stripping tower 9 with extractive distillation column 2 top;
Described alkane water wash column 8 top connects hydrogenator 17 top after connecting hydrogenation input and output material interchanger 18, hydrogenation feed heater 19;
Connect bottom described hydrogenator 17 after hydrogenation input and output material interchanger 18 and connect heat from hydrogenation separating tank 20, heat from hydrogenation separating tank 20 top connects hydrogenation aftercooler 21 successively, add hydrogen-cooled separating tank 23, add hydrogen-cooled separating tank 23 top exit pipeline and be divided into two-way: a road is connected hydrogenation input and output material interchanger 18 after merging with alkane water wash column 8 top exit pipeline after connecting compressor suction tank 24, compressor 25 successively; Another road connects lightness-removing column 29, connects lightness-removing column 29, connect Trimethylmethane finishing column 32 bottom lightness-removing column 29 bottom heat from hydrogenation separating tank 20.
Described extractive distillation column 2 bottom is respectively arranged with extraction Steam reboiler 4, extraction solvent reboiler 5 and extraction intermediate reboiler 6; Extractive distillation column 2 top is provided with evaporator overhead condenser 3; Described Trimethylmethane finishing column 32 bottom arranges intermediate reboiler 33;
Be connected with extractive distillation column 2 top after connecting extraction solvent reboiler 5, extraction intermediate reboiler 6, feed preheater 1, solvent cooler 7 bottom stripping tower 9 successively.
Alkane water wash column 8 is connected solvent recovery tower 14 with bottom alkene water wash column 12, solvent recovery tower 14 top connects Trimethylmethane finishing column intermediate reboiler 33 and solvent recovery tower condenser 15 successively, solvent recovery tower condenser 15 outlet line is divided into two-way: a road returns to solvent recovery tower 14 top, and another road connects extractive distillation column 2 top.
Described hydrogenation feed heater is process furnace.
The separation method preparing Trimethylmethane comprises:
A () unsaturated carbon four enters extractive distillation column after being gasified totally, carry out extracting rectifying by adding solvent, the butane that tower top obtains enters hydrogenation input and output material interchanger after alkane water wash column desolvation;
B () enters stripping tower by the mixture of extracting rectifying tower bottom extraction C 4 olefin and solvent, the C 4 olefin that tower top obtains obtains carbon four monoolefine product again after alkene water wash column desolvation;
C (), by obtaining rich solvent-laden material bottom stripping tower after extraction solvent reboiler, extraction intermediate reboiler, feed preheater heat exchange, returns to extractive distillation column top as solvent feed finally by solvent cooler after being cooled to 50 DEG C; Circulating solvent is extracted a small gangs of material out and is sent to solvent recovery tower simultaneously;
D () saturated carbon four is warming up to 200 DEG C through process furnace again with being mixed into after hydrogenation input and output material interchanger is preheated to 160 DEG C by alkane water wash column top extraction material, finally entering hydrogenator by a small amount of monoolefine and diolefin hydrotreated lube base oil and by micro-organosulfur nitrogen transformation is H
2s and NH
3;
E () is connected with extractive distillation column top as thermal source successively by the circulating solvent of stripping tower reactor extraction after extraction solvent reboiler, extraction intermediate reboiler, feed preheater heat exchange after solvent cooler is cooled to 50 DEG C; Circulating solvent is extracted a small gangs of out and is sent to solvent recovery tower simultaneously;
F () to be merged together with the shallow bid material that circulating solvent is extracted out by the solvent of extraction bottom alkane water wash column, alkene water wash column and the mixture of water send to solvent recovery tower after the heat exchange of solvent recovery tower input and output material interchanger;
(g) by solvent recovery tower top gas phase material through with the heat exchange of Trimethylmethane finishing column intermediate reboiler after be cooled to 70 DEG C by solvent recovery tower condenser after point two-way, one tunnel returns solvent recuperation top of tower as backflow, and extractive distillation column top is sent to as solvent in another road;
(h) hydrogenator bottom discharge through with the heat exchange of hydrogenation input and output material interchanger after enter heat from hydrogenation separating tank; The isolated liquid product of heat from hydrogenation separating tank enters lightness-removing column, and tank top gas phase first enters the further flash distillation of the cold separating tank of hydrogenation after hydrogenation aftercooler is cooled to 40 DEG C;
Add hydrogen-cooled separation tank bottom portion liquid product and return heat from hydrogenation separating tank, a top gas phase part is compressed returns hydrogenation reaction charging as circulating hydrogen, another part sends into the butane contained by the recovery of lightness-removing column top as high pressure exhaust gas, maintains non-hydrogen body burden in recycle hydrogen system stablize with this.
(i) fresh hydrogen is from out-of-bounds merging with the recycle hydrogen adding hydrogen-cooled separating tank top, then after compressor supercharging, enter hydrogenation input and output material interchanger together with C 4 mixture;
J () heat from hydrogenation separating tank bottoms material enters lightness-removing column, by rectifying separation removed overhead H
2s, NH
3with carbon one, carbon two, the third-class non-condensable gas of carbon, bottoms material enters Trimethylmethane finishing column; Trimethylmethane product is obtained by Trimethylmethane finishing column top by rectifying separation.
Described hydrogenator is fixed-bed reactor, and reactor inlet temperature is 200 DEG C, and pressure is 2.5MpaG, and reaction temperature rising is 5 DEG C, and hydrogen-oil ratio is 1.1 (mol ratios), and liquid volume air speed is 2.0h
-1.
Extractive distillation column working pressure: 0.45MPaG, tower top service temperature: 45 DEG C, stage number 120, reflux ratio 3, solvent ratio 7.5;
Stripping tower working pressure: 0.34MPaG, tower top service temperature: 45 DEG C, stage number 50, reflux ratio 2;
Alkane water wash column working pressure: 0.4MPaG, tower top service temperature: 40 DEG C, stage number 60, column internals is sieve plate;
Alkene water wash column working pressure: 0.4MPaG, tower top service temperature: 40 DEG C, stage number 60, column internals is sieve plate;
Solvent recovery tower working pressure: 0.01MPaG, tower top service temperature: 78 DEG C, stage number 45, reflux ratio 3.5;
Lightness-removing column working pressure: 2.0MPaG, tower top service temperature: 56 DEG C, stage number 120, reflux ratio 8.9;
Trimethylmethane finishing column working pressure: 0.5MPaG, tower top service temperature: 45 DEG C, stage number 120, reflux ratio 6.
Adopt flow process as shown in Figure 1, obtain the result of table 2.
Result shows, adopts separation method Trimethylmethane of the present invention, recyclable Trimethylmethane 650kg/h, Trimethylmethane product yield > 99.7%, by heat exchanger network recovered energy, saves energy consumption 0.21kJ/t Trimethylmethane.
Table 2
Claims (8)
1. prepare a device for Trimethylmethane, it is characterized in that:
Described device comprises: extractive distillation column, alkane water wash column, stripping tower, alkene water wash column, solvent recovery tower, hydrogenator, hydrogenation input and output material interchanger, hydrogenation feed heater, hydrogenation tripping device, lightness-removing column, Trimethylmethane finishing column;
Described extracting rectifying top of tower connects alkane water wash column, and extracting rectifying tower bottom connects stripping tower; Stripper top connects alkene water wash column, is connected bottom stripping tower with extractive distillation column top;
Described alkane water wash column top connects hydrogenation input and output material interchanger; Described hydrogenation input and output material heat exchanger exit connects hydrogenator top after connecting hydrogenation feed heater;
Described alkane water wash column is connected solvent recovery tower with bottom alkene water wash column; Solvent recuperation top of tower connects solvent recovery tower condenser after connecting Trimethylmethane finishing column intermediate reboiler again, and solvent recovery tower condensator outlet pipeline is divided into two-way: a road returns to solvent recovery tower top, and another road connects extractive distillation column top;
Hydrogenation tripping device is connected after connecting hydrogenation input and output material interchanger bottom described hydrogenator, hydrogenation separation unit overhead outlet line is divided into two-way, is connected hydrogenation input and output material interchanger after merging after a road connects compressor suction tank, compressor successively with alkane water wash column top exit pipeline; Another road connects lightness-removing column;
Hydrogenation separation unit bottoms connects lightness-removing column; Trimethylmethane finishing column is connected bottom lightness-removing column.
2. prepare the device of Trimethylmethane as claimed in claim 1, it is characterized in that:
Described hydrogenation tripping device comprises heat from hydrogenation separating tank, hydrogenation aftercooler and adds hydrogen-cooled separating tank;
Heat from hydrogenation separating tank is connected after connecting hydrogenation input and output material interchanger bottom described hydrogenator, heat from hydrogenation separating tank top connects hydrogenation aftercooler successively and adds hydrogen-cooled separating tank, add hydrogen-cooled separating tank top exit pipeline and be divided into two-way, one tunnel connects compressor suction tank, another road connects lightness-removing column top, connects lightness-removing column bottom heat from hydrogenation separating tank.
3. prepare the device of Trimethylmethane as claimed in claim 1, it is characterized in that:
Described hydrogenation tripping device comprises: hydrogenation aftercooler and hydrogenation separating tank;
Hydrogenation aftercooler and hydrogenation separating tank is connected successively after connecting hydrogenation input and output material interchanger bottom described hydrogenator, hydrogenation separating tank top exit pipeline is divided into two-way, one tunnel connects compressor suction tank, and another road connects lightness-removing column top, connects lightness-removing column bottom hydrogenation separating tank.
4. the device preparing Trimethylmethane as described in one of claims 1 to 3, is characterized in that:
Described extractive distillation column bottom is respectively arranged with extraction Steam reboiler, extraction solvent reboiler and extraction intermediate reboiler; Extracting rectifying top of tower is provided with evaporator overhead condenser;
Be connected with extractive distillation column top after connecting extraction solvent reboiler, extraction intermediate reboiler, feed preheater, solvent cooler bottom stripping tower successively.
5. prepare the device of Trimethylmethane as claimed in claim 4, it is characterized in that:
Described hydrogenation feed heater is electrical heater or steam pipe oven.
6. adopt the device as described in one of Claims 1 to 5 to prepare a method for Trimethylmethane, it is characterized in that described method comprises:
A () unsaturated carbon four enters extractive distillation column after gasifying and carries out extracting rectifying, the butane that tower top obtains enters hydrogenation input and output material interchanger after alkane water wash column desolvation;
B () enters stripping tower by the mixture of extracting rectifying tower bottom extraction C 4 olefin and solvent, the C 4 olefin that tower top obtains obtains carbon four monoolefine product again after alkene water wash column desolvation;
(c) by the saturated carbon four out-of-bounds come with to be mixed by alkane water wash column top extraction C 4 materials after enter hydrogenation input and output material interchanger, hydrogenation feed heater successively after, enter hydrogenator by a small amount of monoolefine and diolefin hydrotreated lube base oil and remove micro-organosulfur nitrogen impurity;
D () is connected with extractive distillation column top as thermal source successively by the circulating solvent of stripping tower reactor extraction after extraction solvent reboiler, extraction intermediate reboiler, feed preheater heat exchange after solvent cooler is cooled to 40 ~ 60 DEG C; Circulating solvent is extracted a small gangs of material out and is sent to solvent recovery tower simultaneously;
E () to be merged together with the shallow bid material that circulating solvent is extracted out by the solvent of extraction bottom alkane water wash column, alkene water wash column and the mixture of water send to solvent recovery tower after the heat exchange of solvent recovery tower input and output material interchanger;
(f) by solvent recovery tower top gas phase material through with the heat exchange of Trimethylmethane finishing column intermediate reboiler after be cooled to 40 ~ 75 DEG C by solvent recovery tower condenser after point two-way, one tunnel returns solvent recuperation top of tower as backflow, and extractive distillation column top is sent to as solvent in another road;
G () hydrogenator bottom discharge enters hydrogenation tripping device after the heat exchange of hydrogenation input and output material interchanger, an isolated hydrogen part sends into the butane contained by the recovery of lightness-removing column top as high pressure exhaust gas, another part returns to hydrogenator top as recycle hydrogen, and hydrogenation separation unit bottoms material enters lightness-removing column;
H () lightness-removing column bottoms material enters Trimethylmethane finishing column; Trimethylmethane product is obtained by Trimethylmethane finishing column top by rectifying separation.
7. prepare the method for Trimethylmethane as claimed in claim 6, it is characterized in that:
In step (c), mixed c 4 material enters hydrogenator after being heated to 160 ~ 400 DEG C;
In step (g), when hydrogenation tripping device comprises heat from hydrogenation separating tank, hydrogenation aftercooler and adds hydrogen-cooled separating tank, hydrogenator bottom discharge enters heat from hydrogenation separating tank after input and output material heat exchange is cooled to 50 ~ 100 DEG C, heat from hydrogenation separating tank top gas phase enters the cold separating tank of hydrogenation after hydrogenation aftercooler is cooled to 35 ~ 45 DEG C, add the isolated hydrogen part in hydrogen-cooled separating tank top and introduce lightness-removing column top as high pressure exhaust gas, another part enters compressor suction tank, and heat from hydrogenation separating tank bottom liquid phases enters lightness-removing column;
When hydrogenation tripping device comprises hydrogenation aftercooler and hydrogenation separating tank, hydrogenator bottoms material is after input and output material heat exchange, hydrogenation separating tank is entered again after hydrogenation aftercooler is cooled to 35 ~ 45 DEG C, hydrogenation separating tank top portion from hydrogen a part as high pressure exhaust gas introduce lightness-removing column top, another part enters compressor suction tank, and hydrogenation separating tank bottom liquid phases enters lightness-removing column.
8. prepare the method for Trimethylmethane as claimed in claim 6, it is characterized in that:
Described hydrogenator is fixed-bed reactor, and reactor inlet temperature is 160 ~ 400 DEG C, and pressure is 1.5 ~ 4.5MPaG, and reaction temperature rising is 2 ~ 50 DEG C, and hydrogen-oil ratio is 0.2 ~ 5, and liquid volume air speed is 0.5 ~ 6h
-1;
Extractive distillation column working pressure: 0.1 ~ 1MPaG, tower top service temperature: 40 ~ 60 DEG C, stage number 100 ~ 200, reflux ratio 1 ~ 10, solvent ratio 5 ~ 10;
Stripping tower working pressure: 0.1 ~ 1MPaG, tower top service temperature: 40 ~ 60 DEG C, stage number 30 ~ 80, reflux ratio 1 ~ 10;
Alkane water wash column working pressure: 0.1 ~ 1MPaG, tower top service temperature: 35 ~ 50 DEG C, stage number 30 ~ 90, column internals is sieve plate or filler;
Alkene water wash column working pressure: 0.1 ~ 1MPaG, tower top service temperature: 35 ~ 50 DEG C, stage number 30 ~ 90, column internals is sieve plate or filler;
Solvent recovery tower working pressure: 0.005 ~ 0.1MPaG, tower top service temperature: 60 ~ 120 DEG C, stage number 20 ~ 80, reflux ratio 1 ~ 10;
Lightness-removing column working pressure: 1 ~ 3MPaG, tower top service temperature: 20 ~ 100 DEG C, stage number 60 ~ 150, reflux ratio 5 ~ 20;
Trimethylmethane finishing column working pressure: 0.1 ~ 1MPaG, tower top service temperature: 20 ~ 60 DEG C, stage number 80 ~ 150, reflux ratio 1 ~ 10.
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