CN102452888A - Method for refining 1-hexene from fischer tropsch synthetic oils - Google Patents
Method for refining 1-hexene from fischer tropsch synthetic oils Download PDFInfo
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Abstract
The invention discloses a method for refining 1-hexene from fischer tropsch synthetic oils and an equipment system for applying the method. The method comprises the following steps: performing fraction cutting on fischer tropsch synthetic light distillate oil to obtain C6 fraction section; removing oxygen-contained compounds in the C6 fraction through extractive distillation; separating alkanes and olefins of C6 fraction section by an extractive distillation method; performing reactive distillation on the C6 olefins obtained after the extractive distillation, and reacting tertiary carbon olefins of C6 olefins with low carbon alcohol under the action of a catalyst to produce high boiling point ether so as to remove tertiary carbon olefins; removing ethanol left on the C6 olefins by a liquid-liquid extraction method; refining the C6 olefins by a precise distillation method to obtain a 1-hexene product conforming to polymer grade requirements. In comparison with the prior art, the refining technology for the 1-hexene has advantages of scientific and rational design, and high economic benefit.
Description
Technical field
The present invention relates to the synthetic light ends oil treatment process of a kind of oil from Fischer-Tropsch synthesis, particularly Fischer-Tropsch, specifically, the present invention relates to from the synthetic light ends oil of Fischer-Tropsch, extract the method for high purity 1-hexene.
Background technology
Because it is high that energy dilemma and crude oil price continue, synthetic in recent years oil manufacture and following process cause industry member and investigator's extensive concern.Wherein, Fischer-Tropsch synthetic (also claiming F-T synthetic or FTS) oil product gets most of the attention because of the diesel oil that can produce ultra cleaning, high hexadecane value.
At present, for the following process method of oil from Fischer-Tropsch synthesis, mainly concentrate on distillation, the rectifying aspect both at home and abroad.Like patent US7217852, US7294253, AU199951882, US6855248, WO0011113, EP1835011 etc.
For example, patent US7217852 and US7294253 have proposed a kind of distillating method of oil from Fischer-Tropsch synthesis and the intermediate oil of distillation gained, and this intermediate oil contains side chains such as methyl, ethyl, propyl group, and C
9～C
16Ingredients constitute more than 90% of total distillate, this intermediate oil is the staple that constitutes diesel oil, and this intermediate oil has good low-temperature fluidity.
Patent AU199951882, US6855248 and WO0011113 have proposed a kind of distillating method of content of wax Fischer-Tropsch synthesis oil; This method is passed through still column to the Fischer-tropsch derived thing that contains the hydrocarbon of heavy hydrocarbon, light hydrocarbon, middle carbon number; Carry out cut cutting, the carbon number distribution of the product that comes out from still column: lighter hydrocarbons C
23-, middle carbon number hydrocarbon C
20～C
38, heavy hydrocarbon C
30+, obtain useful wax product.
Patent EP1835011 proposes a kind of distillation for processing of Fischer-Tropsch synthetic crude product and the intermediate oil that obtains, and main technique is that the thick product of FTS is cut into petroleum naphtha and intermediate oil, and intermediate oil is used to produce high-quality diesel oil.
Because oil from Fischer-Tropsch synthesis has characteristics such as no sulphur, no aromatic hydrocarbons, normal paraffin, linear alpha-alkene content height; Though its naphtha fraction is not suitable for direct production gasoline because of octane value is low, be the fabulous raw material that separates terminal olefin, lightweight solvent oil and other fine chemicals.
At present, mainly be that South Africa Sasol company is at the linear alpha-alkene of producing based on the Fischer-Tropsch oil product.South Africa Sasol company had been in the Fischer-tropsch process of raw material with the coal in 1994; From be rich in the terminal olefin logistics, isolate products such as 1-amylene, 1-hexene through steps such as prefrationation, selection hydrogenation, washing, etherificate, Methanol Recovery, superfractionation extractive distillation, drying and refinings; Go into operation smoothly, 1-hexene output is above 100,000 tons/year; 1999 and Sasol in 2004 build up the 1-octene device of 4.8 ten thousand tons/year in 2 covers again respectively; Subsequently Sasol company Sai Kuda (Secunda) associated enterprises builds 100,000 tons of/year 1-octene devices in South Africa again, go into operation the second half year in 2007, will make aggregated capacity increase to 19.6 ten thousand tons/year, become the maximum 1-production of octenes merchant in the whole world.From coal-based Fischer-Tropsch oil product, separating the linear alpha-alkene biggest advantage is to be raw material with the coal, reclaims 1-amylene, 1-hexene, 1-octene as by-product, and industrial production cost is low.The Sasol ethylene trimer that extracting 1-hexene adopts than Philips from the thick product of F-T produce the cost of 1-hexene low 40% (people such as Arno de Klerk; Ind.Eng.Chem.Res.; 2007; The 2nd phase, be entitled as " Linear α-olefins from linear internal olefins by a boron-based continuous double-bond isomerization process ").
Terminal olefin is widely used in many fields as comonomer, tensio-active agent synthetic intermediate, plasticizer alcohol, ucon oil and oil dope etc., is the important source material of petrochemical complex.C particularly
6～C
10Even number linear alpha-alkene (1-hexene, 1-octene and 1-decene) because of it special and widely purposes and production technology difficulty height supply falls short of demand especially.The output of China 1-hexene has also satisfied not domestic demand far away.The almost whole dependence on import of the above 1-hexene of domestic polymerization-grade, 1-octene and 1-decene.And it is lower from oil from Fischer-Tropsch synthesis separation of produced terminal olefin cost existing production terminal olefin technology.Therefore, all significant from oil from Fischer-Tropsch synthesis separation of produced high purity 1-hexene at aspects such as alleviation imbalance between supply and demand, raising oil from Fischer-Tropsch synthesis added values.
The object of the invention is exactly through the processing to the FTS oil product, propose a kind of from oil from Fischer-Tropsch synthesis the method for purification 1-hexene.
Go through the synthetic technology that comprises core of exploitation for many years and the indirect coal liquefaction technology of set technique by Zhongke Synthetic Oil Technology Co., Ltd.; Pass through the checking of pilot scale and 160,000 tons of/year demonstration plants, possessed the technical qualification that get into the large industrialized Project design.The present invention select for use based on the Fischer-Tropsch synthesis process of Zhongke Synthetic Oil Technology Co., Ltd. technology and Fischer-Tropsch synthetic iron-based catalyst technology, through in the light ends oil of trial production be raw material; Process exploitation and research that the 1-hexene is purified have been carried out; Propose the practicable 1-hexene purifying technique of a cover, separated the 1-hexene product that obtains meeting the polymerization-grade requirement.
Because the synthetic light ends oil of Fischer-Tropsch is the organic mixture system of a non-constant width of carbon number distribution, forms complicacy, comprises multiple organic cpds such as alkane, alkene, alcohol, aldehyde, ketone, ether, ester, acid simultaneously.Therefore, from Fischer-Tropsch synthesis oil, separating the 1-hexene is a very complicated technology.
Summary of the invention
The purpose of this invention is to provide a kind of method of synthesizing purification 1-hexene the light ends oil from Fischer-Tropsch, it comprises sequential technological processs such as cut cutting, extracting rectifying, liquid-liquid extraction, precise distillation.
Particularly, the invention provides a kind of method of synthesizing purification 1-hexene the light ends oil from Fischer-Tropsch, this method is a raw material with the synthetic light ends oil of Fischer-Tropsch, adopts the cutting of secondary cut to obtain C
6The cut section removes C through extraction fractional distillation earlier
6Organic oxygen-containing compound in the cut is again through extraction fractional distillation, with C
6Cut section alkane separates with alkene; Under catalyst action, make resulting C then
6Tertiary carbon alkene and C in the alkene
1-4Low-carbon alcohol is carried out etherification reaction and is generated high boiling point ether, thereby tertiary carbon alkene is wherein removed, and at last resulting product is further purified through precise distillation, obtains 1-hexene product, and described 1-hexene meets the polymerization-grade requirement.
In aforesaid method of the present invention, carrying out C
6Before the last precise distillation of alkene, preferably, remove and remain in said C earlier through liquid-liquid extraction process
6Low-carbon alcohol component in the alkene, wherein said extraction agent are water.
More specifically, the invention provides a kind of method by the synthetic light ends oil of Fischer-Tropsch purification 1-hexene, this method may further comprise the steps:
(1) the synthetic light ends oil of Fischer-Tropsch is carried out fractionation, cutting obtains C
5 -Cut and C
6 +Cut;
(2) will go up the C that a step obtains
6 +The further fractionation of cut obtains C
6Cut and C
7 +Cut;
(3) will go up the C that a step obtains
6Cut carries out extracting rectifying, as extraction agent, removes wherein contained organic oxygen-containing compound with polar solvent; Wherein said polar solvent as extraction agent can be any in acetonitrile (ACN), N-Methyl pyrrolidone (NMP) or the N (DMF);
(4) will go up the C that a step obtains
6Cut carries out extracting rectifying once more, with C
6Alkane and C
6Alkene separates; Wherein employed extraction agent is ACN, NMP or DMF, and any in the binary mixed solvent that also can form for ACN or NMP and water also can be the double solvents of DMF and salt composition, also can be in the following ionic liquid any: [C
2MIM]
+[BF
4]
-(1-ethyl-3-methyl imidazolium tetrafluoroborate), [C
4MIM]
+[BF
4]
-(1-butyl-3-methyl imidazolium tetrafluoroborate), [C
2MIM]
+[N (CN)
2]
-(1-ethyl-3-Methylimidazole dicyan amine salt), [C
8MIM]
+BF
4]
-(1-octyl group-3-methyl imidazolium tetrafluoroborate) or [C
8Chin]
+[BTA]
-(two (trifluoromethyl sulphonyl) the ammonia salt of 1-octyl group quinoline);
(5) under catalyst action, make C
1-4The C that a low-carbon alcohol and a last step obtain
6Alkene carries out etherification reaction, and tertiary carbon alkene wherein and the reaction of described low-carbon alcohol generate high boiling point ether, are removed through rectifying;
(6) with the above-mentioned C that has removed tertiary carbon alkene
6Olefin stream carries out liquid-liquid extraction, is extraction agent with water, removes and remains in C
6Low-carbon alcohol component in the alkene;
(7) with the above-mentioned C that has removed the low-carbon alcohol component
6Alkene carries out precise distillation, obtains 1-hexene product.
The present invention proposes the imagination of carrying out initial gross separation through the cut cutting earlier, promptly oily through secondary cut from the synthetic next light ends of Fischer-Tropsch, at first cutting obtains C
5 -(comprise C
5Cut) cut and C
6 +(comprise C
6Cut) cut; Then, with C
6 +The cut section is cut once more, obtains C
6Cut and C
7 +(comprise C
7Cut) cut;
Among the application, when mentioning above-mentioned a certain cut, if having the footmark of "+" or "-" on the carbon atom number, its numeral also comprises given figure.
Through the resulting C of cutting twice
6Contain alkane, alkene and organic oxygen-containing compound in the cut section simultaneously.Because organic oxygen-containing compound can form a large amount of azeotropes with hydrocarbon, thereby can not remove through simple distillation method.The present invention proposes with the polar solvent is the extraction fractional distillation of extraction agent, utilizes polar difference between hydro carbons and the organic oxygen-containing compound, with C
6Organic oxygen-containing compound in the cut is removed.Wherein said polar solvent as extraction agent can be selected any of acetonitrile (ACN), N-Methyl pyrrolidone (NMP) or N (DMF) etc. for use, preferred NMP.In the description of this paper, the employed extraction agent of this step is also referred to as extraction agent 1.
After removing organic oxygen-containing compound, C
6Only contain C in the cut
6Alkane and alkene.Because there are polarity difference in alkene and alkane, so can adopt the method for extracting rectifying to separate.During the hydrocarbon component is separated at present there be solvent commonly used: acetonitrile (ACN), N-Methyl pyrrolidone (NMP), N (DMF).ACN and NMP can improve separation efficiency through adding a certain amount of water; DMF can improve separation efficiency through the extractive distillation with salt method with salt binding such as KSCN.
In the method for the invention, said C
6C in the cut
6The available extraction agent that separates of alkane and alkene is among ACN, NMP or the DMF any; Also can be in ACN and water binary mixed solvent or NMP and the water binary mixed solvent any; Also the double solvents that DMF and salt are formed can be, also in the following ionic liquid any can be: [C
2MIM]
+[BF
4]
-(1-ethyl-3-methyl imidazolium tetrafluoroborate), [C
4MIM]
+[BF
4]
-(1-butyl-3-methyl imidazolium tetrafluoroborate), [C
2MIM]
+[N (CN)
2]
-(1-ethyl-3-Methylimidazole dicyan amine salt), [C
8MIM]
+[BF
4]
-(1-octyl group-3-methyl imidazolium tetrafluoroborate), [C
8Chin]
+[BTA]
-(two (trifluoromethyl sulphonyl) the ammonia salt of 1-octyl group quinoline).
In above-mentioned extraction agent, the massfraction of water is 1～45% in the binary mixed solvent that is made up of ACN or NMP and water; Preferred massfraction is 10%.
In above-mentioned extraction agent, comprise the double solvents that DMF and salt are formed, wherein said salt can be inorganic salt, for example thiocyanate-, preferably KSCN, NaSCN etc.
In the description of this paper, the employed extraction agent of this step is also referred to as extraction agent 2.Most preferred extraction agent 2 is binary mixed solvents that NMP and water are formed.
Carrying out C
6The alkane alkene after separating of cut is only contained C
6The logistics of alkene, because 1-hexene and its isomer boiling point are approaching, polarity is approaching, and is particularly more approaching with the tertiary carbon alkene with carbon number, the boiling-point difference of its boiling point and 1-hexene becomes problematic component maximum in the purification 1-hexene process about 1 ℃.Wherein said tertiary carbon alkene is meant said C
6Contained carbonatoms is all tertiary carbon alkene of 6 in the olefin fraction, includes but not limited to 2-ethyl-1-butylene, 2-Methyl-1-pentene.The present invention utilizes tertiary carbon alkene and low-carbon alcohol under the effect of catalyzer, to react and generates high boiling point ether, and the principle that other olefin isomer and alkane do not react with alcohol is removed C
6The most approaching in the alkene mixture, the most difficult tertiary carbon olefin component of removing with 1-hexene boiling point.
Employed catalyzer is a strongly acidic cationic exchange resin in above-mentioned etherification reaction, preferably uses the Amberlyst series product, more preferably Amberlyst 15 or Amberlyst 35; Employed low-carbon alcohol is C
1-4Alcohol comprises the monohydroxy-alcohol of the straight or branched with 1-4 carbon atom, and for example methyl alcohol, ethanol, propyl alcohol, Virahol or propyl carbinol etc. preferably use methyl alcohol or ethanol, more preferably use ethanol.
Obtain C by above step
6The ether that tertiary carbon alkene and low-carbon alcohol generate, this product can be used as cleaning, the stop bracket gasoline additive, therefore can improve the added value of product of this technical process.
Need to prove that described etherification reaction process has very strict restriction to water, because water is easy under the effect of catalyzer and the tertiary carbon olefine reaction generates tertiary carbon alcohol, so, carrying out will carrying out C earlier before the etherification reaction rectification method takes off tertiary carbon alkene
6The dehydration of alkene, described dehydration can be adopted conventional chemical technique, and for example described dehydration can be selected methods such as rectifying tower stripping, absorption for use.
Removed C in above step
6Behind the tertiary carbon alkene in the olefin stream, utilize the difference of boiling point between 1-hexene and its isomeric component, the present invention selects for use directly through the method purification 1-of precise distillation hexene; Before this, preferably can be at first with the C that removes tertiary carbon alkene
6Low-carbon alcohol such as ethanol component remaining in the alkene are removed; Particularly, can water be extraction agent, through liquid-liquid extraction process, remove and remain in C
6Low-carbon alcohol component in the alkene.
Use the 1-hexene product that method of the present invention obtains and meet the polymerization-grade requirement.
Another object of the present invention has provided a kind of device systems, but uses the said method of synthesizing purification 1-hexene the light ends oil from Fischer-Tropsch of this system's embodiment of the present invention.Said device systems comprises secondary cut Cutting Tap, secondary extractive distillation column, etherification reaction rectifying tower and precise rectification tower.Preferably, device systems of the present invention also comprises with the matching used two groups of solvent recovery towers of secondary extractive distillation column and for removing the C that obtains behind the etherification reaction
6Remaining low-carbon alcohol in the alkene and the liquid-liquid extraction unit that is provided with.
Particularly, device systems of the present invention mainly comprises following equipment: 1# Cutting Tap, 2# Cutting Tap, 1# extractive distillation column and 1# solvent recovery tower, 2# extractive distillation column and 2# solvent recovery tower, etherification reaction rectifying tower, liquid-liquid extraction unit and precise rectification tower.
Preferably, in order to ensure carrying out smoothly of etherification reaction process described in the etherificate distillation column reactor, before getting into the etherification reaction rectifying tower, earlier with described C
6Alkene dewaters through dewatering unit, and this dewatering unit can be selected devices such as rectifying tower stripping tower or adsorption tower for use.
Compared with prior art, the purify method of 1-octene of the present invention has following advantage:
(1) binary mixed solvent that the binary mixed solvent of ACN or NMP and water being formed, particularly NMP and water are formed is used to contain the extraction agent of the alkane alkene sepn process of alkane and alkene, can reduce solvent ratio greatly, the saving cost;
(2) C
6Removing of tertiary carbon alkene selected the etherification reaction rectification method for use in the olefin isomer, solved the difficult isolating problem of tertiary carbon alkene, resulting C
6The ether that tertiary carbon alkene and low-carbon alcohol generate can be used as cleaning, the stop bracket gasoline additive, therefore can improve the added value of product of this technical process, practiced thrift cost, and reduced energy consumption;
(3) whole 1-hexene purifying technique, science, rationally, economic benefit is high.
Description of drawings:
Accompanying drawing 1 is the process flow diagram of purification 1-hexene from the synthetic light ends oil of Fischer-Tropsch.
In this accompanying drawing, wherein each Reference numeral provided the main streams that equipment according to the invention relates to:
1 is the logistics of Fischer-Tropsch synthetic light ends oil, and 2 is C
5 -The component logistics, 3 is C
6 +The component logistics, 4 is C
6The component logistics, 5 is C
7 +The component logistics, 6 for not containing the C of organic oxygenatedchemicals
6Hydrocarbon stream, 7 is the mixture stream passes of extraction agent 1 and organic oxygen-containing compound, 8 is the organic oxygen-containing compound logistics; 9 extraction agent 1 logistics for recovery; 10 is fresh extraction agent 1 logistics, and 11 is extraction agent 1 logistics that 9 and 10 mixing backs get into the 1# extractive distillation column, and 12 is C
6The alkane logistics, 13 is extraction agent 2 and C
6The mixture stream passes of alkene, 14 is C
6Olefin stream, 15 extraction agent 2 logistics for recovery, 16 is fresh extraction agent 2 logistics, and 17 is extraction agent 2 logistics that 15 and 16 mixing backs get into the 2# extractive distillation columns, and 18 is water-free C
6Olefin stream, 19 is water, 20 for removing the C of tertiary carbon alkene
6Olefin stream, 21 is C
6Tertiary carbon alkene in the alkene and low-carbon alcohol reaction generate the logistics of high boiling point ether, and 22 for remove the C of tertiary carbon alkene
6Alkene cooling logistics, 23 for removing the C after the residual ethanol
6Olefin stream, 24 is 1-hexene product stream, 25 is the olefin isomer logistics; 26 for having absorbed the logistics of alcoholic acid extraction agent water, and 27 is second alcohol and water azeotrope stream, and 28 for reclaiming the pure water logistics that obtains from conical settling tank; 29 is the make up water logistics, and 30 is the logistics of 28,29 and 34 mixed extraction agent water, the 31 straight alcohol logistics for recovery; 32 is the mixture stream passes of water and terepthaloyl moietie, and 33 is ethylene glycol stream, and 34 for reclaiming the pure water logistics that obtains from the glycol recovery tower; 35 is the fresh ethanol logistics, and 36 is 31 and 35 mixed ethanol stream.
Embodiment
Further explain method and apparatus of the present invention below with reference to accompanying drawing 1.
Shown in accompanying drawing; The equipment that technical process according to the invention relates to comprises 1# Cutting Tap, 2# Cutting Tap, 1# extractive distillation column and 1# solvent recovery tower, 2# extractive distillation column and 2# solvent recovery tower, water trap, etherification reaction rectifying tower, water cooler, liquid-liquid extraction unit and precise rectification tower, and utility appliance conical settling tank, ethanol regenerating column and glycol recovery tower.
More specifically, the unitary technical indicator of each major equipment of device systems according to the invention is:
(1) number of theoretical plate of 1# Cutting Tap is 10～50, is preferably 30; Reflux ratio is 1～20, is preferably 4; Tower still temperature is 115～128 ℃, is preferably 122 ℃; The preferred tower medium position of feed entrance point, for example when number of theoretical plate was 30, feed entrance point was preferably at the 17th block of plate (from top to bottom); Atmospheric operation;
(2) number of theoretical plate of 2# Cutting Tap is 10～50, is preferably 30; Reflux ratio is 1～20, is preferably 4; Tower still temperature is 135～148 ℃, is preferably 140 ℃; The preferred tower medium position of feed entrance point, for example when number of theoretical plate was 30, feed entrance point was preferably at the 17th block of plate (from top to bottom); Atmospheric operation;
(3) 1# extractive distillation column number of theoretical plate is 15～65, preferred 40; Reflux ratio is 0.5～8, preferred 1; Solvent ratio is 0.5～10, preferred 3; C
6The cut feed entrance point is 30～60% places (from top to bottom) of tower height, and the extractant feed position is for being 5%～20% place (from top to bottom) of tower height; Employed extraction agent is acetonitrile (ACN), N-Methyl pyrrolidone (NMP) or N (DMF) etc., and preferred extraction agent is NMP;
1# solvent recovery tower number of theoretical plate is 10～50, and is preferred 30, and reflux ratio is 1～20, preferred 6;
(4) 2# extractive distillation column number of theoretical plate is 40～120, preferred 80; Reflux ratio is 0.5～8, preferred 3; Solvent ratio is 1～20, preferred 5; The binary mixed solvent that preferred NMP of extraction agent and water are formed, the massfraction of water is 1～45% in the binary mixed solvent that NMP and water are formed, and is preferably 10%;
2# solvent recovery tower number of theoretical plate is 10～50, and is preferred 30, and reflux ratio is 0.5～8, preferred 2;
(5) dewater earlier before the etherification reaction carrying out; Etherification reaction rectifying tower number of theoretical plate is 10～50, preferred 35; Reflux ratio is 0.8～20, preferred 4; Working pressure is 0.05～0.5MPa (absolute pressure); In the tower in low-carbon alcohol and the raw material mol ratio of tertiary carbon alkene be 1～20, preferred 5; Employed C in the etherification reaction rectifying tower
1-4Low-carbon alcohol, preferred alcohol; Employed catalyzer is a strongly acidic cationic exchange resin, and preferred catalyzer is the Amberlyst series product, for example Amberlyst 15 or Amberlyst35;
(6) liquid-liquid extraction Element Theory plate number is 2～40, and is preferred 10, and solvent ratio is 0.5～8, preferred 2, and service temperature is 20～100 ℃, preferred normal temperature; And/or
(7) the precise rectification tower number of theoretical plate is 30～150, and is preferred 80, and reflux ratio is 2～40, preferred 12.
In aforesaid device of the present invention system, the technical process of purification 1-hexene is following:
(1) the synthetic light ends oil of Fischer-Tropsch gets into 1# Cutting Tap middle part, obtains C from the cat head cutting
5 -(comprise C
5Cut) cut obtains C at the bottom of tower
6 +(comprise C
6Cut) cut;
(2) from the C at the bottom of the 1# cutting Tata
6 +The cut section gets into 2# Cutting Tap middle part, obtains C from 2# Cutting Tap cat head
6Cut obtains C at the bottom of tower
7 +(comprise C
7Cut) cut;
(3) under the effect of extraction agent, will be from the C of 2# Cutting Tap cat head
6The cut section is removed organic oxygen-containing compound wherein through the 1# extracting rectifying;
(4) make the above-mentioned C that removes organic oxygen-containing compound
6Cut gets into the 2# extractive distillation column, through extraction fractional distillation with C
6Alkane and C
6Alkene separately;
(5) C that comes from the 2# extractive distillation column
6Alkene gets into the etherification reaction rectifying tower, under catalyst action, makes C
6Tertiary carbon alkene in the alkene and low-carbon alcohol reaction generate high boiling point ether, and are removed;
(6) removed the C of tertiary carbon alkene
6Olefin stream gets into the liquid-liquid extraction unit, through being that the liquid-liquid extraction method of extraction agent is removed and remained in C with water
6Low-carbon alcohol component in the alkene; With
(7) removed the C of low-carbon alcohol
6Olefin stream gets into precise rectification tower, obtains meeting the 1-hexene product of polymerization-grade requirement from the precise distillation column overhead.
More specifically, in aforesaid device of the present invention system, the technical process of purification 1-hexene is following:
Get into 1# Cutting Tap middle part from Fischer-Tropsch synthetic light ends oil logistics 1, be C by the logistics that obtains at the bottom of the tower 3
6 +Component, overhead stream 2 is C
5 -Component;
Make logistics 3 get into 2# Cutting Tap middle part, obtain logistics 4 from cat head and be C
6Component, the logistics 5 that obtains at the bottom of the tower is C
7 +Component;
Make logistics 4 get into the 1# extractive distillation column, utilize polar difference between hydrocarbon and the organic oxygen-containing compound, remove C
6Organic oxygen-containing compound in the cut, logistics 6 is not for containing the C of organic oxygenatedchemicals
6Hydrocarbon makes it get into alkane alkene separating unit, carries out separating of alkane and alkene; Logistics 7 is the mixture of extraction agent and organic oxygen-containing compound, gets into the 1# solvent recovery tower, reclaims the extractant stream 9 that obtains, and returns the 1# extractive distillation column and recycles through replenishing 10 formation blended extraction agent (also the claiming extraction agent 1) logistics 11 of fresh extraction agent; The logistics 8 that obtains from 1# solvent recuperation column overhead is organic oxygen-containing compound;
Make the C that does not contain organic oxygenatedchemicals
6Hydrocarbon stream 6 gets into the 2# extractive distillation column, through with the binary extraction agent extraction fractional distillation of (also claiming extraction agent 2), obtains C from cat head
6Alkane logistics 12 obtains extraction agent and C at the bottom of tower
6The mixture stream passes 13 of alkene; Logistics 13 gets into the 2# solvent recovery tower; The extractant stream 15 that obtains reclaiming at the bottom of the tower, logistics 15 is returned the 2# extractive distillation column and is recycled through replenishing fresh extraction agent 16 back formation blended extraction agent (also claiming extraction agent 2) logistics 17;
The C that 2# extracting rectifying column overhead is obtained
6 Olefin stream 14 gets into water trap, removes and remains in C
6The moisture content (logistics 19) of alkene the inside; Make water-free C
6Olefin stream 18 gets into the etherification reaction rectifying tower, under the effect of catalyzer, and C
6Tertiary carbon alkene in the alkene and low-carbon alcohol (following description is example with ethanol) reaction generates high boiling point ether logistics 21, at the bottom of tower, removes; Removed the C of tertiary carbon alkene
6The mixture flow 20 of alkene and excess ethyl alcohol is discharged from cat head, after water cooler is cooled to room temperature, forms the C after lowering the temperature
6It is the liquid-liquid extraction unit of extraction agent (30 are the logistics of extraction agent water) that olefin stream 22 gets into water, the C of the residual low-carbon alcohol that is removed
6 Olefin stream 23;
Make to remove and remain in C
6C behind the ethanol in the alkene
6Olefin stream 23 gets into precise rectification tower, obtains meeting the 1-hexene product stream 24 of polymerization-grade requirement from the precise distillation column overhead;
The absorption that the liquid-liquid extraction unit is come the extractant stream 26 of residual ethanol be delivered to conical settling tank and reclaim second alcohol and water wherein; The pure water logistics 28 that obtains at the bottom of the tower; Mix the logistics 3 that the back forms extraction agent water with make up water logistics 29, rework solution liquid extraction cells recycles;
Obtain second alcohol and water azeotrope stream 27 from the conical settling tank cat head and get into the ethanol regenerating column; Under the effect of extraction agent terepthaloyl moietie (logistics 33); The straight alcohol logistics 31 that obtains reclaiming from ethanol regenerating column cat head is returned the etherification reaction rectifying tower and is recycled through replenishing fresh ethanol (logistics 35) back formation blended ethanol stream 36;
From the water that obtains at the bottom of ethanol reclaims Tata and the mixture stream passes 32 entering glycol recovery towers of terepthaloyl moietie; The recovery ethylene glycol stream 33 that obtains at the bottom of the glycol recovery Tata is returned the ethanol regenerating column and is recycled, and the water rework solution liquid extraction cells that obtains from the glycol recovery column overhead is as the extraction agent recycle.
Preferably, the major equipment of device systems of the present invention moves according to following technical qualification:
The number of theoretical plate of 1# Cutting Tap is 10～50, and is preferred 30, and reflux ratio is 1～20, preferred 4, the preferred tower medium position of feed entrance point, preferred the 17th block of plate (from top to bottom), atmospheric operation;
The number of theoretical plate of 2# Cutting Tap is 10～50, and is preferred 30, and reflux ratio is 1～20, preferred 4, the preferred tower medium position of feed entrance point, preferred the 17th block of plate (from top to bottom), atmospheric operation;
The number of theoretical plate of 1# extractive distillation column is 15～65, and is preferred 40, and reflux ratio is 0.5～8; Preferred 1, solvent ratio is 0.5～10, preferred 3; C6 cut feed entrance point is 30～60% places (from top to bottom) of tower height, and the extractant feed position is for being 5%～20% place (from top to bottom) of tower height;
The number of theoretical plate of 1# solvent recovery tower is 10～50, and is preferred 30, and reflux ratio is 1～20, preferred 6;
The number of theoretical plate of 2# extractive distillation column is 40～120, and is preferred 80, and reflux ratio is 0.5～8, preferred 3, and solvent ratio is 1～20, preferred 5, and quality content is 1～45% in the extraction agent;
The number of theoretical plate of 2# solvent recovery tower is 10～50, and is preferred 30, and reflux ratio is 0.5～8, preferred 2;
The etherification reaction Rectification Column's Theoretical Plate Number is 10～50, and is preferred 35, and reflux ratio is 0.8～20, preferred 4, and working pressure is 0.05～0.5MPa (absolute pressure), in the tower in low-carbon alcohol and the raw material mol ratio of tertiary carbon alkene be 1～20, preferred 5; And dewater earlier before the etherification reaction carrying out;
The unitary number of theoretical plate of liquid-liquid extraction is 2～40, and is preferred 10, and solvent ratio is 0.5～8, preferred 2, and service temperature is 20～100 ℃, preferred normal temperature; And/or
The number of theoretical plate of precise rectification tower is 30～150, and is preferred 80, and reflux ratio is 2～40, preferred 12.
Illustrate in greater detail technical scheme of the present invention through specific examples below, the embodiment that is provided only is used for example the present invention, the protection domain that does not limit the present invention in any way.
According to flow process shown in Figure 1, the synthetic light ends oil of Fischer-Tropsch logistics 1 entering number of theoretical plate is 35 1# Cutting Tap, and reflux ratio is 4, and feed entrance point is 19 blocks of plates (from top to bottom, down together), can at the bottom of 1# cuts Tata, obtain C
6 +Cut logistics 3, purity reaches 99.95%, and the recovery reaches 99.97%; C
6 +Cut entering number of theoretical plate is 35 2# Cutting Tap, and reflux ratio is 4, and feed entrance point is 19 blocks of plates, can obtain C from cat head
6Component logistics 4.
Above-mentioned C
6Cut logistics 4 entering are that the number of theoretical plate of extraction agent is 40 1# extractive distillation column with NMP, utilize polar difference between hydrocarbon and the organic oxygen-containing compound, remove C
6Organic oxygen-containing compound in the cut, reflux ratio are 1, solvent ratio is 3, C
6The cut feed entrance point is the 20th a block of plate, and the NMP feed entrance point is the 6th a block of plate, and the logistics 6 that obtains from 1# extracting rectifying column overhead is the C that does not contain organic oxygenatedchemicals
6Hydrocarbon, logistics 6 gets into alkane alkene separating unit, and logistics 7 is the mixture of NMP and organic oxygen-containing compound; The entering number of theoretical plate is 30 1# solvent recovery tower; Reflux ratio is 6, and feed entrance point is the 7th a block of plate, reclaims the NMP logistics 9 that obtains; After replenishing extraction agent, return the 1# extractive distillation column and recycle, the logistics 8 that obtains from 1# solvent recuperation column overhead is organic oxygen-containing compound.
Make the said C that does not contain organic oxygenatedchemicals
6Hydrocarbon stream 6 gets into the 2# extractive distillation columns, and number of theoretical plate is 80, reflux ratio is 3, solvent ratio is 5, C
6The hydrocarbon feed entrance point is that the 52nd plate, extractant feed position are that quality content is 10% in the 3rd block of plate, the extraction agent, through being the extraction fractional distillation of extraction agent with NMP and water, obtains C from cat head
6Alkane logistics 12 obtains extraction agent and C at the bottom of tower
6The mixture stream passes 13 of alkene; Logistics 13 gets into the 2# solvent recovery tower; Number of theoretical plate is 30, reflux ratio is 2, feed entrance point is 15, and the extractant stream 15 that obtains at the bottom of the 2# solvent recuperation Tata is returned the 2# extractive distillation column and recycled after replenishing extraction agent, the C that obtains from cat head
6Olefin stream 14 gets into water trap, removes and remains in C
6The moisture content of alkene the inside.
Make said water-free C
6Olefin stream 18 gets into the etherification reaction rectifying tower, and number of theoretical plate is 35, reflux ratio is 4, the mol ratio of ethanol and tertiary carbon alkene 2-ethyl-1-butylene is 5, atmospheric operation, under the effect of catalyst A mberlyst 15, and C
6Tertiary carbon alkene 2-ethyl-1-butylene in the alkene and low-carbon alcohol ethanol synthesis generate high boiling point ether ethyl uncle hexyl ether logistics 21, at the bottom of tower, remove, and have removed the C of tertiary carbon alkene
6Alkene and excess ethanol logistics 20 go out from cat head.
Make the said C that removes tertiary carbon alkene
6Alkene and excess ethanol logistics 20 are after water cooler is cooled to room temperature, and getting into water is the liquid-liquid extraction unit of solvent, and liquid-liquid extraction tower number of theoretical plate is 10, solvent ratio is 2, removes through the liquid-liquid extraction unit and remains in C
6Ethanol in the alkene.
Make said having removed remain in C through the liquid-liquid extraction unit
6C behind the ethanol in the alkene
6Olefin stream 23; Get into precise rectification tower; The precise rectification tower number of theoretical plate is 80, reflux ratio is 12, feed entrance point is the 40th a block of plate, obtains meeting the 1-hexene product stream 24 of polymerization-grade requirement from the precise distillation column overhead, and the recovery of 1-hexene and purity all reach 99%.
The absorption that comes from the liquid-liquid extraction unit alcoholic acid extractant stream 26; Get into conical settling tank; The conical settling tank number of theoretical plate is that number of theoretical plate is 40, reflux ratio is 3, feed entrance point is the 30th a block of plate; From reclaiming the pure water logistics 28 that obtains at the bottom of the Tata, rework solution liquid extraction cells recycles after make up water; The second alcohol and water azeotrope stream 27 that obtains from the conical settling tank cat head gets into the ethanol regenerating column; Ethanol regenerating column number of theoretical plate is 30, solvent ratio is 2, reflux ratio is 3, second alcohol and water feed entrance point is that the 23rd plate, terepthaloyl moietie feed entrance point are the 4th block of plate; Under the effect of extraction agent terepthaloyl moietie; Obtain straight alcohol logistics 31 from ethanol regenerating column cat head, after replenishing ethanol, return the etherification reaction rectifying tower and recycle; From the water that obtains at the bottom of ethanol reclaims Tata and the mixture stream passes 32 of terepthaloyl moietie; Get into the glycol recovery tower; Glycol recovery tower number of theoretical plate is 15, reflux ratio is 2, feed entrance point is the 7th a block of plate; The ethylene glycol stream 33 that obtains at the bottom of the glycol recovery Tata is returned the ethanol regenerating column and is recycled, the also rework solution liquid extraction cells recycle of water that obtains from the glycol recovery column overhead.
Main streams analytical data in the table 11-hexene purifying technique
Be illustrated more clearly in the advantage of the inventive method and equipment by above embodiment, can find out C by above data
6Organic oxygen-containing compound ratio and tertiary carbon alkene in the olefin fraction are removed effectively, and the purity of resulting 1-hexene is 99%, can reach the requirement to polymerization single polymerization monomer purity.
Below described embodiment of the present invention in detail, can do a lot of improvement and variation obviously for a person skilled in the art and can not deviate from essence spirit of the present invention.All these variations and improvement are all within protection scope of the present invention.
Claims (10)
1. the method for a purification 1-hexene from oil from Fischer-Tropsch synthesis, this method is a raw material with the synthetic light ends oil of Fischer-Tropsch, adopts the method for secondary cut cutting to obtain C
6The cut section removes C with polar solvent extract rectifying earlier
6Organic oxygen-containing compound in the cut, again with extraction fractional distillation with C
6Cut section alkane separates with alkene; Under catalyst action, make resulting C then
6Tertiary carbon alkene in the alkene and low-carbon alcohol are carried out etherification reaction and are generated high boiling point ether, thereby can described tertiary carbon alkene be removed, and resulting product is further purified through precise distillation, obtain meeting the 1-hexene product of polymerization-grade requirement.
2. purify the according to claim 1 method of 1-hexene, this method may further comprise the steps:
(1) the synthetic light ends oil of Fischer-Tropsch is carried out fractionation, cutting obtains C
5 -Cut and C
6 +Cut;
(2) will go up the C that a step obtains
6 +The further fractionation of cut obtains C
6Cut and C
7 +Cut;
(3) will go up the C that a step obtains
6Cut carries out extracting rectifying, as extraction agent, removes wherein contained organic oxygen-containing compound with polar solvent; Wherein said polar solvent as extraction agent can be any among ACN, NMP or the DMF;
(4) will go up the C that a step obtains
6Cut carries out extracting rectifying once more, with C
6Alkane and C
6Alkene separates; Wherein employed extraction agent is ACN, NMP or DMF, and any in the binary mixed solvent that also can form for ACN or NMP and water also can be the double solvents of DMF and salt composition, also can be in the following ionic liquid any: [C
2MIM]
+[BF
4]
-, [C
4MIM]
+[BF
4]
-, [C
2MIM]
+[N (CN)
2]
-, [C
8MIM]
+[BF
4]
-Or [C
8Chin]
+[BTA]
-
(5) under catalyst action, make C
1-4The C that a low-carbon alcohol and a last step obtain
6Alkene carries out etherification reaction, and tertiary carbon alkene wherein and the reaction of described low-carbon alcohol generate high boiling point ether, are removed through rectifying;
(6) with the above-mentioned C that has removed tertiary carbon alkene
6Olefin stream carries out liquid-liquid extraction, is extraction agent with water, removes and remains in C
6Low-carbon alcohol component in the alkene;
(7) with the above-mentioned C that has removed the low-carbon alcohol component
6Alkene carries out precise distillation, obtains 1-hexene product.
3. like the method for the said purification 1-of claim 2 hexene, in the binary mixed solvent that wherein described extraction agent ACN of step (4) or NMP and water are formed, the massfraction of water is 1～45%, and the massfraction of preferably water is 10%.
4. like the method for the said purification 1-of claim 2 hexene, wherein the extraction agent described in the step (4) comprises the double solvents that DMF and salt are formed, and wherein said salt is KSCN or NaSCN.
5. like the method for the said purification 1-of claim 2 hexene, wherein, the etherification reaction rectification method that carries out step (5) carries out C before removing tertiary carbon alkene earlier
6The dehydration of alkene; Preferred wherein said C
6The dehydration of alkene selects for use the method for rectifying tower stripping or absorption to carry out.
6. like the method for the said purification 1-of claim 2 hexene; Wherein the employed catalyzer of step (5) is a strongly acidic cationic exchange resin; Preferred described strongly acidic cationic exchange resin is the Amberlyst series product, and more preferably described strongly acidic cationic exchange resin is Amberlyst 15 or Amberlyst35; Wherein said low-carbon alcohol is methyl alcohol or ethanol, and preferred low-carbon alcohol is an ethanol.
7. like the method for the said purification 1-of claim 2 hexene, wherein carry out C in step (7)
6Before the last precise distillation of alkene, at first remove and remain in said C through liquid-liquid extraction process
6Contained low-carbon alcohol component in the alkene, wherein said extraction agent is a water.
8. one kind is used for implementing the device systems of claim 1-7 from oil from Fischer-Tropsch synthesis purification 1-hexene, and said device systems comprises secondary cut Cutting Tap, secondary extractive distillation column, etherification reaction rectifying tower, liquid-liquid extraction unit and precise rectification tower; Preferred said device systems also comprises and the matching used two groups of solvent recovery towers of secondary extractive distillation column.
9. device systems according to claim 8, wherein said device systems mainly comprises following equipment: 1# Cutting Tap, 2# Cutting Tap, 1# extractive distillation column and 1# solvent recovery tower, 2# extractive distillation column and 2# solvent recovery tower, etherification reaction rectifying tower, liquid-liquid extraction unit and precise rectification tower; The technical indicator of wherein said equipment is:
(1) number of theoretical plate of 1# Cutting Tap is 10～50, and reflux ratio is 1～20, and tower still temperature is 115～128 ℃, and feed entrance point is the tower medium position;
(2) number of theoretical plate of 2# Cutting Tap is 10～50, and reflux ratio is 1～20, and tower still temperature is 135～148 ℃, and feed entrance point is the tower medium position;
(3) 1# extractive distillation column number of theoretical plate is 15～65, and reflux ratio is 0.5～8, and solvent ratio is 0.5～10;
(4) 1# solvent recovery tower number of theoretical plate is 10～50, and reflux ratio is 1～20;
(5) 2# extractive distillation column number of theoretical plate is 40～120, and reflux ratio is 0.5～8, and solvent ratio is 1～20;
(6) 2# solvent recovery tower number of theoretical plate is 10～50, and reflux ratio is 0.5～8;
(7) the etherification reaction Rectification Column's Theoretical Plate Number is 10～50, and reflux ratio is 0.8～20, and working pressure is 0.05～0.5MPa (absolute pressure), in the tower in low-carbon alcohol and the raw material mol ratio of tertiary carbon alkene be 1～20;
(8) solvent selected for use of liquid-liquid extraction unit is a water; The unitary number of theoretical plate of liquid-liquid extraction is 2～40, and solvent ratio is 0.5～8, and service temperature is 20～100 ℃; And/or
(9) number of theoretical plate of precise rectification tower is 30～150, and reflux ratio is 2～40;
Preferably, the technical indicator of wherein said each equipment is:
(1) number of theoretical plate of 1# Cutting Tap is 30, and reflux ratio is 4, and tower still temperature is 122, and feed entrance point is the 17th (from top to bottom) in tower middle part;
(2) number of theoretical plate of 2# Cutting Tap is 30, and reflux ratio is 4, and tower still temperature is 140, and feed entrance point is the 17th (from top to bottom) in tower middle part;
(3) number of theoretical plate of 1# extractive distillation column is 40, and reflux ratio is 1, and solvent ratio is 3, and extraction agent is NMP;
(4) number of theoretical plate of 1# solvent recovery tower is 30, and reflux ratio is 6;
(5) number of theoretical plate of 2# extractive distillation column is 80, and reflux ratio is 3, and solvent ratio is 5, and extraction agent is NMP and water, and wherein the massfraction of water is 10%;
(6) number of theoretical plate of 2# solvent recovery tower is 30, and reflux ratio is 2;
(7) the etherification reaction Rectification Column's Theoretical Plate Number is 35, and reflux ratio is 4, the mol ratio 5 of tertiary carbon alkene in low-carbon alcohol and the raw material in the tower;
(8) liquid-liquid extraction Element Theory plate number is 10, and solvent ratio is 2, and service temperature is a normal temperature; And/or
(9) the precise rectification tower number of theoretical plate is 80, and reflux ratio is 12.
10. like claim 8 or 9 any device systems, the idiographic flow from the synthetic light ends oil product purification 1-hexene of Fischer-Tropsch that carries out therein is:
(1) makes the synthetic light ends oil of Fischer-Tropsch get into 1# Cutting Tap middle part, obtain C from the cat head cutting
5 -(comprise C
5Cut) cut obtains C at the bottom of tower
6 +Cut;
(2) from the C at the bottom of the 1# cutting Tata
6 +The cut section gets into 2# Cutting Tap middle part, obtains C from 2# Cutting Tap cat head
6Cut obtains C at the bottom of tower
7 +Cut;
(3) from the C of 2# Cutting Tap cat head
6The cut section is removed organic oxygen-containing compound wherein through the 1# extractive distillation column, has obtained removing the C of oxygenatedchemicals from 1# extracting rectifying column overhead
6Cut, distilled is the mixture of extraction agent and oxygenatedchemicals at the bottom of the tower, makes the latter get into the 1# solvent recovery tower and carries out solvent recuperation;
(4) remove the C of organic oxygen-containing compound through above-mentioned extractive distillation column
6Cut gets into the 2# extractive distillation column, again through extracting rectifying, with C
6Alkane and C
6Alkene separately obtains C from cat head
6Alkane obtains extraction agent and C at the bottom of tower
6The mixture of alkene; The latter gets into the 2# solvent recovery tower, obtains C
6Alkene, and reclaim solvent;
(5) C that a step is obtained
6Alkene gets into the etherification reaction rectifying tower, under the effect of catalyzer strongly acidic cationic exchange resin, makes said C
6Tertiary carbon alkene and C in the alkene
1-4Low-carbon alcohol is carried out etherification reaction and is generated high boiling point ether, separates and removes resulting ether;
(6) removed the C of tertiary carbon alkene
6Olefin stream gets into the liquid-liquid extraction unit, through being that extraction agent is removed and remained in C with water
6Ethanol component in the alkene; With
(7) make and removed alcoholic acid C
6Olefin stream gets into precise rectification tower, obtains meeting the 1-hexene product of polymerization-grade requirement from the precise distillation column overhead.
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Address after: 101407 Beijing city Huairou District Yanqi Economic Development Zone C District No. 1 south two Street Park Applicant after: Synefuels China Inc. Applicant after: Zhongke Synthetic Oil Technology Co., Ltd. Address before: 100195 Haidian District, Beijing, North Village, a road, a static core Park, block N Applicant before: Synefuels China Inc. Applicant before: Zhongke Synthetic Oil Technology Co., Ltd. |
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Application publication date: 20120516 |