CN102718617B - System and method for refining isobutane - Google Patents
System and method for refining isobutane Download PDFInfo
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- CN102718617B CN102718617B CN201110428567.5A CN201110428567A CN102718617B CN 102718617 B CN102718617 B CN 102718617B CN 201110428567 A CN201110428567 A CN 201110428567A CN 102718617 B CN102718617 B CN 102718617B
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Abstract
The invention relates to a system and a method for refining isobutane. The system for refining isobutane comprises a crude rectification device, an adsorption device, a hydrogenation reaction device and a re-rectification device. The crude rectification device, the adsorption device, the hydrogenation reaction device and the re-rectification device are connected orderly by pipes. The adsorption device is a dimethyl ether adsorption tank. A dimethyl ether adsorbent is loaded in the dimethyl ether adsorption tank. The hydrogenation reaction device comprises a hydrogenation reactor. A hydrogenation feeding pump is connected to a hydrogenation feeding heat exchanger. The hydrogenation feeding heat exchanger is connected to an inlet of the hydrogenation reactor. An outlet of the hydrogenation reactor is connected to a gas-liquid separation tank. The method provided by the invention utilizes a preliminary rectification-adsorption removal combined technology to realize removal of alcohols and ethers, utilizes a preliminary rectification-hydrogenation reaction combined technology to realize removal of 1-butene, so that reasonable control of an equipment investment and an operation cost is realized, and reduces an operation cost of pre-rectification and improves a product yield by about 5% because of the transformation of all 1-butene and butadiene into n-butane in hydrogenation.
Description
Technical field
The present invention relates to Trimethylmethane purification techniques, particularly relate to essence and relate to Trimethylmethane refining system and process for purification.
Background technology
The refining production technology of domestic existing Trimethylmethane is take pre-desulfurization, dry and rectification process as main; High density polyethylene(HDPE) is not high to isobutane feedstock purity requirement at present, and >=89%, foreign matter content requires very high, wherein 1-butylene content≤97PPm, divinyl≤3PPm; Alcohol compound≤6PPm; Simple employing rectificating method, needs more than 100 number of theoretical plates at de-ether and methanol column, and reflux ratio is more than 40; As a same reason, the facility investment of debutenizer and process cost increase severely; And often product purity will be brought up to 95%, even more than 99.5%, foreign matter content could conformance with standard.Overall operation expense increases by 1.5～2 times, and operation easier increasing, and in product, foreign matter content easily exceeds standard
Summary of the invention
In my company's Trimethylmethane production equipment, through studying well experiment, done very large novelty and improved, concrete technical scheme is as follows;
A kind of Trimethylmethane refining system of the present invention, comprises thick rectifier unit, adsorption unit, hydrogenation reaction device and rectifier unit again; Thick rectifier unit, adsorption unit, hydrogenation reaction device are connected by pipeline successively with rectifier unit again; Adsorption unit is dme adsorption tanks, and dme sorbent material is housed in adsorption tanks; Hydrogenation reaction device comprises hydrogenator, connects hydrogenation feed exchanger by hydrogenation fresh feed pump, and hydrogenation feed exchanger connects hydrogenator entrance; Hydrogenator material outlet connects knockout drum.
Described thick rectifier unit comprises de-dme tower and debutenizer; Rectifier unit comprises lightness-removing column again; Dme tower, debutenizer and lightness-removing column are packing tower; Filler is the flat ring-like random packing random packing of QH-3-25.
Adopt system of the present invention to carry out the process for purification of Trimethylmethane, step is as follows:
1) enter thick rectifier unit from the thick Trimethylmethane mixture of upstream MTBE/1-butene units: through rectifying separation, most of light constituent flows out from tower top in tower; Trimethylmethane and the extraction at the bottom of tower of 1-butylene rich solution; The rich solution that autospasy dme tower bottom flow goes out enters debutenizer top, and in tower, through rectifying, the 1-butylene rich solution going out from tower bottom flow is sent to outside battery limit (BL) after cooling; The Trimethylmethane rich solution that tower top distillates is from sending into adsorption unit;
2) now the dme of remnants can be through the dme adsorption tanks absorption of adsorption unit, and the liquid after the dme adsorption tanks absorption of adsorption unit is sent to hydrogenation reaction device;
3) being mixed into from the material of dme adsorption tanks and hydrogenation circulation fluid the material that hydrogenation fresh feed pump entrance is forced into 2.0～3.0MPaG mixes with new hydrogen, then in hydrogenation feed exchanger and hot water heat exchange, after heat exchange, temperature reaches the requirement of hydrogenation temperature, enters hydrogenator after heat exchange; In hydrogenator, alkene is under the effect of catalyzer, and hydrogen reaction generation Trimethylmethane and normal butane, removes other impurity; Hydrogenation products enters water cooler cooling water condensation to 20～40 ℃ again and enters knockout drum; Separate the hydrogen torch that reduces internal heat; A part is returned to hydrogenation fresh feed pump entrance as circulation fluid and is mixed with fresh feed, and a part of liquid enters rectifier unit lightness-removing column again through interchanger heat exchange to 45～62 ℃;
4) in lightness-removing column through rectifying, remove light constituent after Trimethylmethane go out from tower bottom flow; Refining Trimethylmethane after adsorption treatment enters Trimethylmethane tank storage tank.
Described sorbent material is that SQ-112 type oxygen-bearing organic matter removes agent
Described catalyzer is HTC Ni 400RP 2.5mm catalyzer.
Technique effect of the present invention is:
1, adopt preliminary rectifying to remove alcohol and ether in conjunction with the mode of adsorbing and removing;
2, adopt preliminary rectifying in conjunction with hydrogenation reaction, 1-butylene to be removed; Facility investment and process cost (reflux ratio is only 20 left and right) are rationally controlled; And because all 1-butylene and divinyl are converted into normal butane by hydrogenation process, the process cost that has reduced preorder rectifying makes again product yield improve 5% left and right.
3, in carbon four hydrogenation techniques, use first HTC Ni 400RP 2.5mm, through my company's production test repeatedly, initiated the carbon four hydrogenation production technique of low temperature, low pressure, high conversion (being 100% at present).And this catalyzer initial investment is few, long service life.
4, more than 99.5% Trimethylmethane of DNA purity in carbon four hydrocarbon feeds, does cooling agent for high density polyethylene device.This technology also can be applicable to produce by general carbon four hydrocarbon the Trimethylmethane that different purity requires.
Accompanying drawing explanation
Fig. 1 (a): technical process leading portion schematic diagram of the present invention,
Fig. 1 (b): back segment intention is shown in technical process of the present invention.
Embodiment
This example is our concrete engineering project, and has produced and reached good effect:
As Fig. 1 (a) (b) as shown in, system of the present invention is: Trimethylmethane refining system, comprises thick rectifier unit, adsorption unit, hydrogenation reaction device and rectifier unit again; It is characterized in that thick rectifier unit, adsorption unit, hydrogenation reaction device are connected by pipeline successively with rectifier unit again; Adsorption unit is dme adsorption tanks, and dme sorbent material is housed in adsorption tanks; Hydrogenation reaction device comprises hydrogenator, connects hydrogenation feed exchanger by hydrogenation fresh feed pump, and hydrogenation feed exchanger connects hydrogenator entrance; Hydrogenator material outlet connects knockout drum.
1. first adopt two step rectification methods to improve the content of Trimethylmethanes, it is reached more than 90%, raw material is first removed light constituent-propane and dme at de-dme tower, then enters debutenizer and remove most of alkene; The butylene by product separating can return to MTBE/1-butene units, as the supplementary raw material of this device.
Secondly 2. adopt hydrogenation method, in fixed bed hydrogenation reactor, residual olefin is thoroughly converted into alkane (being mainly normal butane) under the effect of hydrogenation catalyst, and then the light constituents such as hydrogen are removed with lightness-removing column; Now isobutane purity is more than 90%.
3. for isobutane purity is further improved, need be by Trimethylmethane obtained in the previous step rectifying again, its overhead product is the Trimethylmethane that purity is greater than 99.5%.
4. last refining with adsorbents, in fixed-bed adsorber, remove minor amount of water and the micro-dme in product with the sorbent material (SQ112) of 3A molecular sieve and de-oxygen-containing organic compound, remove Determination of Trace Sulfur in product etc. with ZnO sweetening agent as sulphur content exceeds standard.
(2) Technology source
The domestic packaged process without similar fairly large production high purity Trimethylmethane, the technology of the present invention is to form through our innovation research, rectifying tower adopts the filler of Ze Hua engineering corporation of Tsing-Hua University; Hydrogenation catalyst adopts the full hydrogenation catalyst of carbon four liquid phase of Beijing Chemical Research Institute of China Petrochemical Industry.
It is simple that this technique has process, invest little, operational condition relax, the feature that dry gas yied is low.Be applicable to produce pure Trimethylmethane (> 90%) product of special procuring.Can obtain good economic benefit.
(3) technological process
Illustrate:
One, thick distillation system: this flow process belongs to general distillation process, but has selected the random packing of the QH-3 of Tsing-Hua University type at each rectifying tower, and 0.3 meter of most effective height equivalent to one theoretical plate (HETP), is the half of general random packing height equivalent to one theoretical plate (HETP) in random packing; By calculating, calculate by 60 theoretical stages, bed stuffing height only needs 20 meters, and common fillers needs 40 meters, filler in whole tower is to pass through grid support, filling 4 meters of high fillers, above add compression grid, is sparger above, 5 layers of filler, the in the situation that of equal height, realize higher separation efficiency, can make reflux ratio reduce and ease down to 23, the corresponding decline 20～30% of energy consumption by 40.With domestic other process using poor efficiency fillers or more compared with the sieve-tray tower of poor efficiency, greatly reduce the height of tower and the expense of capital construction, and its high efficiency is brought the reduction of process cost.
From the pressurization of thick Trimethylmethane mixture process P-101 pump, the preheating of E-101 feed heater of upstream MTBE/1-butene units, under bubble point temperature, enter de-dme tower (C-101) top.In tower, through rectifying separation, most of light constituent (dme, propane etc.) flows out from tower top, and tower top pressure is at 0.6～0.85MPaG.Remove Trimethylmethane and the extraction at the bottom of tower of 1-butylene rich solution after light constituent.
The rich solution that autospasy dme tower bottom flow goes out enters debutenizer (C-102) top, tower reactor liquid steam heating to 40～60 ℃, and in tower, through rectifying, the 1-butylene rich solution going out from tower bottom flow is sent to outside battery limit (BL) after cooling.The Trimethylmethane rich solution that removes butylene distillates from tower top, enters return tank D103, sends into dme adsorption tanks (D-109C/D) through pump P103 through overhead condenser E102, and this sorbent material is housed in adsorption tanks
Two, oxygen-bearing organic matter removes:
Be sent to and add hydrogen partial through dme adsorption tanks (D-109C/D), now remaining dme can be adsorbed by dme sorbent material, the application of this sorbent material in this flow process belongs to first, that the product SQ-112 of University of Petroleum type oxygen-bearing organic matter removes agent, make de-dme tower number of theoretical plate reduce 1/3, energy consumption reduces 30%, and the while can be adsorbed the oxygen-bearing organic matter impurity such as the methyl alcohol of butadiene product equipment generation, there is good adsorption effect, organic impurities is reached below 10PPm.
Three, hydrogenation reaction system:
Being mixed into from the material of dme adsorption tanks (D-109C/D) and hydrogenation circulation fluid the material that hydrogenation fresh feed pump (P-106) entrance is forced into 2.0～3.0MPaG mixes with new hydrogen, then in hydrogenation feed exchanger (E-108) and hot water heat exchange, after heat exchange, temperature can reach require 25～45 ℃ of hydrogenation temperature, under normal operation, do not need heater heats, after heat exchange, enter hydrogenator (R-101).In hydrogenator, alkene is under the effect of catalyzer, and hydrogen reaction generation Trimethylmethane and normal butane, and can remove other impurity.
Hydrogenation products enters water cooler (E-109) again and enters knockout drum (D-105) with cooling water condensation to 20～40 ℃.Separate the hydrogen torch that reduces internal heat; A part is returned to hydrogenation fresh feed pump (P-106) entrance as circulation fluid and is mixed with fresh feed, and a part of liquid enters lightness-removing column C-103 through E-110 with hot water heat exchange to 45～62 ℃.
Hydrogenation reaction technique also belongs to domestic the first, and old technical process is owing to can not finding suitable catalyzer to have to abandon hydrogenation process, so also need rectifying, facility investment is large, and butylene thoroughly can not be removed.Because of the quite difficulty that separates of butylene and Trimethylmethane.Even if found domestic existing palladium series catalyst, prices are rather stiff for it, and temperature of reaction pressure approaches 4.0MPa, and temperature of reaction is more than 100 ℃, and Static Equipment pressure rating is high, and the energy consumption of reaction needed is high; Through repeatedly investigating, (the HTC Ni 400RP concrete title of 2.5mm catalyzer and the Johnson Matthey Catalysts of the producer village believe that ten thousand rich (Shanghai) are applied to this technique to take new catalyst, owing to having optimized proportioning, reaction activity is strong, 30～40 ℃ of desired reaction temperatures, approach normal temperature, and energy consumption is extremely low, reaction pressure 1.5～2.5MPa, greatly reduces facility investment and operational risk.And transformation efficiency can be up to 100%.This catalyzer is also that first Application is in C4 complete processing.
Four, distillation system again:
This flow process belongs to general distillation process, but select the random packing of the QH-3 of Tsing-Hua University type at each rectifying tower, in random packing, 0.3 meter of most effective height equivalent to one theoretical plate (HETP), greatly reduce the height of tower and the expense of capital construction, and its high efficiency is brought the reduction of process cost.Domestic other process using poor efficiency fillers or the more sieve-tray tower of poor efficiency.
At lightness-removing column (C-103), tower reactor material, through hot water heating to 45～65 ℃, through rectifying, separates light constituent from tower top in tower, delivers to flare system.After removing light constituent, Trimethylmethane goes out from tower bottom flow.Bottom product order after Trimethylmethane water cooler (E-113) is cooling enters two adsorption tanks, for 3A molecular sieve adsorption, remove minor amount of water, smart Trimethylmethane after adsorption treatment enters Trimethylmethane tank D-108, is then intermittently sent to the smart Trimethylmethane storage tank to high density polyethylene(HDPE) outside battery limit (BL) by take away pump P-108.
Above example has illustrated flow process of the present invention, technique and effect, and the present invention is our current production equipment, and all work well now, have reached international and domestic advanced level.
Trimethylmethane refining system and process for purification that the present invention proposes, be described by embodiment, person skilled obviously can change making method as herein described in content of the present invention, spirit and scope or suitably change and combination not departing from, and realizes technology of the present invention.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the artly, they are deemed to be included in spirit of the present invention, scope and content.
Claims (2)
1. a Trimethylmethane refining system, comprises thick rectifier unit, adsorption unit, hydrogenation reaction device and rectifier unit again; It is characterized in that thick rectifier unit, adsorption unit, hydrogenation reaction device are connected by pipeline successively with rectifier unit again; Adsorption unit is dme adsorption tanks, SQ-112 type oxygen-bearing organic matter is housed removes the dme sorbent material of agent in adsorption tanks; Hydrogenation reaction device comprises hydrogenator, is filled with HTC Ni400RP2.5mm catalyzer in hydrogenator; Connect hydrogenation feed exchanger by hydrogenation fresh feed pump, hydrogenation feed exchanger connects hydrogenator entrance; Hydrogenator material outlet connects knockout drum; Thick rectifier unit comprises de-dme tower and debutenizer; Rectifier unit comprises lightness-removing column again; Dme tower, debutenizer and lightness-removing column are packing tower; Filler is the flat ring-like random packing of QH-3-25.
2. adopt the system of claim 1 to carry out the process for purification of Trimethylmethane, it is characterized in that step is as follows:
1) enter thick rectifier unit from the thick Trimethylmethane mixture of upstream MTBE/1-butene units: through rectifying separation, most of light constituent flows out from tower top in tower; Trimethylmethane and the extraction at the bottom of tower of 1-butylene rich solution; The rich solution that autospasy dme tower bottom flow goes out enters debutenizer top, and in tower, through rectifying, the 1-butylene rich solution going out from tower bottom flow is sent to outside battery limit (BL) after cooling; The Trimethylmethane rich solution that tower top distillates is from sending into adsorption unit;
2) now the dme of remnants can be through the dme adsorption tanks absorption of adsorption unit, and the liquid after the dme adsorption tanks absorption of adsorption unit is sent to hydrogenation reaction device;
3) being mixed into from the material of dme adsorption tanks and hydrogenation circulation fluid the material that hydrogenation fresh feed pump entrance is forced into 2.0～3.0MPaG mixes with new hydrogen, then in hydrogenation feed exchanger and hot water heat exchange, after heat exchange, temperature reaches the requirement of hydrogenation temperature, enters hydrogenator after heat exchange; In hydrogenator, alkene is under the effect of catalyzer, and hydrogen reaction generation Trimethylmethane and normal butane, removes other impurity; Hydrogenation products enters water cooler cooling water condensation to 20～40 ℃ again and enters knockout drum; Separate the hydrogen torch that reduces internal heat; A part is returned to hydrogenation fresh feed pump entrance as circulation fluid and is mixed with fresh feed, and a part of liquid enters rectifier unit lightness-removing column again through interchanger heat exchange to 45～62 ℃;
4) in lightness-removing column through rectifying, remove light constituent after Trimethylmethane go out from tower bottom flow; Refining Trimethylmethane after adsorption treatment enters Trimethylmethane storage tank.
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| CN104030876B (en) * | 2013-03-04 | 2016-06-15 | 中国石化工程建设有限公司 | A kind of extracting rectifying and hydrogenation combination technique prepare the system and method for Trimethylmethane |
| CN104276917B (en) * | 2013-07-09 | 2016-03-16 | 中国石化工程建设有限公司 | A kind of combination process prepares the system and method for Trimethylmethane |
| CN104276916B (en) * | 2013-07-09 | 2016-03-16 | 中国石化工程建设有限公司 | A kind of system and separation method preparing Trimethylmethane |
| CN103773498B (en) * | 2013-11-28 | 2015-09-02 | 山东海成石化工程设计有限公司 | The high temperature hydrogenation purification process of liquefied gas material |
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| FR2695635A1 (en) * | 1992-09-14 | 1994-03-18 | Inst Francais Du Petrole | Prodn. of isobutane from 4C hydrocarbon mixt - comprising distillation, adsorption-desorption and isomerisation steps |
| CN101671221A (en) * | 2009-09-17 | 2010-03-17 | 茂名实华东成化工有限公司 | Preparation method of polymer solvent iso-butane |
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