CN100430353C - Method of separating butane-1 from C4 fraction - Google Patents
Method of separating butane-1 from C4 fraction Download PDFInfo
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- CN100430353C CN100430353C CNB2006101615738A CN200610161573A CN100430353C CN 100430353 C CN100430353 C CN 100430353C CN B2006101615738 A CNB2006101615738 A CN B2006101615738A CN 200610161573 A CN200610161573 A CN 200610161573A CN 100430353 C CN100430353 C CN 100430353C
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Abstract
The invention discloses a separating method of butane-1 from C4 distillate, which is characterized by the following: adopting mixed C4 distillate with isobutene as raw material; using complex compound of Bronzed acid and Lewis acid as initiator; transmitting isobutene in the C4 distillate into polyisobutene; removing isobutene; transmitting tail gas C4 into rectifying system to separate; obtaining polymer grade butane-1 product.
Description
Technical field
The present invention relates to C
4The fraction separation method is specifically related to a kind of from C
4The method of separating butane-1 in the cut.
Background technology
C
1Fraction separation is to produce the polymerization-grade butene-1, and comprehensive utilization is made good use of C
4The important prerequisite of resource.Because C1 cut component is more, boiling point is approaching, and particularly the boiling point of iso-butylene and butene-1 only differs from 0.6 degree, and only relying on rectifying is impossible obtain the polymerization-grade butene-1, also will rely on chemical method or chemical method to separate with physics method bonded method.In the existing separation method, mainly contain sulfuric acid process, trimethyl carbinol method, etherification method, oligomerisation method, adsorption method of separation, isomerate process etc.
Sulfuric acid process is industrial widely used older method, and all there is industrialized unit in a lot of countries, as the U.S., France, Britain industrialization technology are arranged all, can obtain purer iso-butylene with this method.Because isobutene conversion is not very high, so still have more iso-butylene in the butene-1 cut that obtains, is difficult to obtain pure butene-1, also have equipment corrosion and problem of environmental pollution bigger.
Trimethyl carbinol method is that spent ion exchange resin is made initiator, makes mixed C
4In iso-butylene and water reaction, generate the trimethyl carbinol, the trimethyl carbinol separates the back catalytic dehydration can get highly purified iso-butylene.Because conversion for isobutene is also not too high, is difficult to obtain pure butene-1.
Adsorption method of separation is the novel method that the seventies occurs, and this method is to utilize C
4The difference of hydrocarbon molecule radius size or on the molecular sieve surface difference of physical adsorption power, use molecular sieve to be sorbent material, selectively adsorb straight chain hydrocarbon, thereby reach positive structure hydrocarbon and the isolating purpose of isomeric hydrocarbon, can obtain highly purified iso-butylene and butene-1 by rectifying again.The characteristics of this method are that service temperature is low, the process side reaction seldom, starting material and general facilities consumption are few, pollute for a short time, do not have corrosion.But this method equipment complexity, technical difficulty is big, and industrialized production is difficult for realizing.
The oligomerisation method is to use acidic ion exchange resin, heteropolyacid etc. as initiator, makes C
1Iso-butylene generation oligomerisation reaction in the cut generates low-molecular-weight materials such as dimerization and trimerization, unreacted C
1Cut carries out rectification process, obtains highly purified butene-1.The isobutene dimer of gained and trimer can be as the additive or the industrial chemicals that improve gasoline octane rating.Because the temperature of oligomerisation reaction is higher, works as C
1When middle isobutylene concentration is higher, reacts very fierce and be difficult to control, this method relatively is suitable for the lower C of iso-butylene content
1The further purifying of cut.Remove as iso-butylene in the one-stage process MTBE device exhaust.
Etherification method is the developed method along with a large amount of uses of gasoline high-octane number component methyl tertiary butyl ether (MTBE) in recent years, and at present domestic existing more than 30 cover full scale plants are to make the extensively industrial route of employing of polymerization-grade butene-1 both at home and abroad, and it is to utilize C
1The reaction of iso-butylene and methyl alcohol generates MTBE in the cut, and the nonreactive characteristics of other alkene are removed iso-butylene.The C that does not contain iso-butylene
4, separate the butene-1 that obtains polymerization-grade purity by superfractionation.The characteristics of this technology are that the utilization of resources is abundant, the reaction conditions gentleness, and equipment does not have corrosion.But this method technical process is long, and remaining iso-butylene still need carry out dimerization reaction to be removed, and the divinyl in the raw material also need carry out hydrogenation reaction to be removed, and the economic worth of the MTBE of coproduction is not high.
Summary of the invention
The present invention will solve is exactly the problem that above-mentioned prior art exists, and provides a kind of new for C
1The method of separating butane-1 in the cut.
The present invention adopts following technical scheme:
Utilize iso-butylene very easily to carry out this characteristic of cationic polymerization, with the mixed C that contains iso-butylene
1Cut is a raw material, and the complex compound that uses the formation of bronsted acid and Lewis acid makes C as initiator
1Iso-butylene in the cut all is converted into polyisobutene, removes the polymerization reaction end gas C behind the iso-butylene
4Be sent to distillation system again and separate, obtain polymerization-grade butene-1 product.
The main technique step of the method for the invention is:
Mixed C
1Cut feeds in the polymerization reactor after through rectifying or drying and dehydrating, and the initiator that under agitation adds some amount in proportion reacts, and the reaction times is 30～180 minutes, and temperature of reaction is-35～40 ℃.Reaction adds the terminator termination reaction after finishing, and uses alkali lye to neutralize, destroy unnecessary initiator, water is washed again, and washing afterreaction mixture enters in decarburization four towers and separates, carbon four tail gas of cat head enter the superfractionation system, tell the butene-1 of polymerization-grade.The thick polyisobutene of tower still obtains the polyisobutene product through steps such as atmospheric and vacuum distillation, filtrations.Two kinds of values of the product are all very high.
Mixed C used in the present invention
4Cut is the light C of catalytic cracking
1Raw material or cracking C
1Raffinate.
The initiator that polymerization technique of the present invention uses mainly is the complex compound that bronsted acid (Bronsted acids) and Lewis acid (Lewis acids) form, as water, HCl, alcohol, halohydrocarbon and AlCl
3, BF
3And the complex compound that forms such as tin, titanium, plumbous halogenide or aluminum alkyls.
As raw material C
4In when containing micro-moisture, can directly use the solid, powdery aluminum chloride as initiator because the initiator activity of solid state is relatively poor, large usage quantity, the usage ratio of initiator and raw material are 1～3% (wt).In order to improve catalyst activity, AlCl
3, BF
3And alkyl aluminum chloride can make the liquid complexing initiator in advance and use, and the usage quantity reduction ratio greatly of such initiator is 0.1～1.0% (wt).
The size of determining to depend primarily on desired product polyisobutene molecular weight of temperature of reaction of the present invention, if the polyisobutene product (molecular weight 10000～60000) of molecular weight in expecting, temperature of reaction can be controlled in-35～-10 ℃; If expect low-molecular-weight polyisobutene product (molecular weight is below 10000), temperature of reaction can be controlled in-10～40 ℃.
The polyreaction of iso-butylene is the chain reaction that is caused by cationic initiator, reacts very quick.Consider the factor of mass transfer aspect, the reaction times was controlled at 30～180 minutes usually, was preferably 40～120 minutes.
Pressure is very little to the influence of polyreaction.Usually reaction is to maintain under the pressure that makes reaction mass keep liquid phase to carry out, and is generally 0～0.5MPa.
Technology of the present invention can be used polymerization technique one time, also can adopt after polymerization technology.One time polymerization technique is under the condition in the reaction times of using many slightly initiators and growing slightly, makes the iso-butylene in the carbon four reach most conversion.The product polyisobutene molecular weight distribution that obtains like this is wide slightly, and quality is slightly poor, but can be suitable for doing purposes such as tackifier.And after polymerization technology is to make polyreaction divide secondary to carry out, make in the polyreaction in the first time and to be no more than 95% iso-butylene and to have participated in polyreaction, after telling unreacted carbon four gases, carry out the polyreaction second time again, the whole polyreactions of iso-butylene are wherein fallen.Polyisobutene product molecular weight distribution by after polymerization reaction gained is narrow, and quality is better, and product has purposes widely.
In two kinds of carbon four raw materials commonly used, butene-1 and iso-butylene content all are much higher than the content in the catalytic cracking C-4-fraction in the cracking c_4 cut, the former is more suitable for producing isobutene polymer grade-1 in being used to separate C-4-fraction, and the typical case of C-4-fraction forms listed as table 1:
Table 1C
4The typical case's composition of cut and the Main physical character of each component
| Component | Take out surplus cracking C 1Content (v%) | Catalysis C 1Content (v %) | Boiling point ℃ 760mmHg | Relative volatility |
| C 3 | 0.74 | 1.5 | - | - |
| Trimethylmethane | 0.70 | 50.8 | -11.7 | 1.20 |
| Normal butane | 2.87 | 2.77 | -0.5 | 0.87 |
| Iso-butylene | 35.94 | 26.00 | -6.9 | 1.07 |
| Anti-butylene | 11.92 | 1.38 | 0.9 | 0.85 |
| Maleic | 7.51 | - | 3.6 | 0.8 |
| Butene-1 | 39.95 | 17.55 | -6.3 | 1.04 |
| Divinyl | 0.2 | - | -4.4 | 1.00 |
Produce in the technology of butene-1 at etherification method, the divinyl in carbon four raw materials can not participate in etherification reaction, and behind the etherification reaction, the content back of divinyl increases to some extent.Because the boiling point of divinyl and butene-1 is more approaching, and divinyl is the impurity that influences the butene-1 quality product, must remove.Usually need to install the selective hydrogenation device in the etherification method, cause the increase of investment, and the yield of butene-1 is descended, and in the technology of polymerization legal system butene-1, because divinyl can participate in polymerization, most divinyl can be removed.Thereby can increase hydrogenator, and help the raising of butene-1 yield.
Another shortcoming of etherification method is that conversion for isobutene is not really high, the content of iso-butylene is still higher in the reaction end gas, in the tail gas of the etherification technology of common reclaiming type, usually still also have an appointment about 0.2% iso-butylene, still need to add and build the device that cover oligomerisation or a dimerization removed remaining iso-butylene, this also needs to increase investment.And the technology of polymerization legal system butene-1 is because conversion for isobutene is higher, and the amount of residual iso-butylene seldom unnecessaryly remakes the processing that further removes the iso-butylene step in the tail gas.
The polyisobutene of the technology gained of polymerization legal system butene-1 is the general product of having many uses, and it changes processing condition according to the needs in market, can obtain the product of different polymerization degree.The production that is used for clean disperser for lubricating oil, transformer oil, hydraulic fluid, glue paste, tenderizer that low-molecular-weight polyisobutene is a large amount of.In the polyisobutene of molecular weight can be used as the tackifier, tackiness agent, seal gum, calking agent etc. of lubricating oil.
The technology of polymerization legal system butene-1 of the present invention is compared with the technology that etherification method is produced butene-1, it can obtain two kinds of product of higher value simultaneously, the value of the joint product polyisobutene of its gained is higher than the value of the joint product MTBE of etherification method gained, thereby the economic benefit of device is better.In polymerization technology,, remain in C because conversion for isobutene is very high
1Iso-butylene content in the cut is very low, does not need dimerization or oligomerisation reaction device further to remove remaining iso-butylene.In polymerization technology, because divinyl can most ofly participate in polyreaction in the raw material, butadiene content is very low in the tail gas, thereby need not set up hydrogenator in order to remove divinyl.Like this appliance arrangement still less, flow process is shorter, helps saving investment.
Embodiment
Embodiment 1
With 200ml process 4A molecular sieve drying, (light carbon four raw materials of catalytic cracking are v) packed in the there-necked flask of a 500ml to contain iso-butylene and be 25%, exterior cooling is carried out in the cryostat that adds dry ice with ethanol, when temperature in the bottle reaches-35 ℃, under agitation with the AlCl of syringe with 0.7ml
3Aromatic hydrocarbons complexing initiator dropwise evenly adds, 120 minutes reaction times, reaction finishes the back and adds a spot of ethanol stopped reaction, add the dilution of 50～100ml sherwood oil again, after this thick polymers solution process washing, the vacuum-drying, obtain the transparent polyisobutene product of water white transparency or little Huang, molecular weight product is 35000.Conversion for isobutene is 100%.The content of iso-butylene is zero through the chromatogram detection in the tail gas, and the content of butene-1 is changed to 24.7% by 18.7% before reacting.This cut can be told the butene-1 of polymerization-grade owing to do not contain iso-butylene by superfractionation.
Embodiment 2
Make use-case 1 described raw material through the 4A molecular sieve drying, in a volume through particular design is 30 liters polymeric kettle, carried out the successive polymerization test, method is the said initiator in input raw material and the example 1 in polymeric kettle of continous-stable, their input speed is respectively 15 liters/hour and 60 milliliters/hour, and air speed is 0.5 o'clock
-1, temperature of reaction is-35 ℃, and through 11 hours continuous operation, post-processing step was with example 1, and reaction back conversion for isobutene can reach more than 99% molecular weight product average out to 45000.The content of iso-butylene in tail gas can reach 0.2～0.4%, and this tail gas also can obtain the butene-1 of polymerization-grade by superfractionation.
Embodiment 3
250ml is 40% (cracking carbon-4 feedstock is v) packed one into as described in Example 1 in the experimental installation through the iso-butylene that contains of molecular sieve drying, adopt same experiment and post-processing step, the initiator that uses still is aromatic hydrocarbons complexing initiator, add-on is 1.5ml, reaction times is 1.5 hours, and temperature of reaction is-20 ℃.After the reaction, isobutene conversion in the raw material reaches 100%, and iso-butylene reacts completely in the tail gas, and the molecular weight of products obtained therefrom polyisobutene is 12000, and the content of n-butene-1 34.38% changes into 56.82% before react, and this tail gas can be used for the production of polymerization-grade butene-1.
Embodiment 4
Experiment condition and experimental technique are with example 1, what initiator used is alkyl aluminum chloride, additional proportion is 3 ‰, after the reaction, the content of iso-butylene by the reaction before 15.0% vanishing, transformation efficiency 100%, gained polyisobutene molecular weight product is 10000, and the content of butene-1 becomes 32.1% by 29.5% before reacting, and this tail gas can be used for the production of polymerization-grade butene-1 equally.
Embodiment 5
Experimental Establishment and experimental technique are with example 1, and the initiator of use is an aluminum chloride aromatic hydrocarbons complexing initiator, and the initiator additional proportion is 5 ‰, and temperature of reaction is 35 ℃.After the reaction, the content of iso-butylene is converted into zero by 38.63% before reacting, and the molecular weight of gained polyisobutene product is 1426.The content of butene-1 becomes 55.82% by 34.63% before reacting, divinyl contained in the raw material has also participated in reaction in reaction, its content becomes 0.05% by 1.10% before reacting, and transformation efficiency reaches 95%, also approaches the requirement that tail gas is used to produce the polymerization-grade butene-1.
Embodiment 6
Experimental Establishment and experimental technique are with example 5, and the initiator additional proportion is 6 ‰, and temperature of reaction is 15 ℃, and the content of reaction back iso-butylene is converted into zero by 38.63% before reacting, and the molecular weight of gained polyisobutene product is 4100.The content of butene-1 becomes 55.29% by 34.63% before reacting, and this tail gas also can be used for the production of polymerization-grade butene-1.
Claims (10)
1, a kind of from C
4The method of separating butane-1 in the cut is characterized in that with the mixed C that contains iso-butylene
4Cut is a raw material, and the complex compound that uses the formation of bronsted acid and Lewis acid makes C as initiator
4Iso-butylene in the cut all is converted into polyisobutene, removes the polymerization reaction end gas C behind the iso-butylene
4Be sent to distillation system again and separate, obtain polymerization-grade butene-1 product; The complex compound that aforementioned bronsted acid and Lewis acid form comprises water, HCl, alcohol, halohydrocarbon and AlCl
3, BF
3And tin, titanium, the halogenide of lead or the complex compound that aluminum alkyls forms.
2, described according to claim 1 from C
4The method of separating butane-1 is characterized in that mixed C in the cut
4Cut is after the process drying and dehydrating, feed in the polymerization reactor, under agitation add initiator and carry out polyreaction, reaction adds the terminator termination reaction after finishing, and in the adding alkali lye and unnecessary initiator, water cleans again, and washing afterreaction mixture enters in decarburization four towers and separates, carbon four tail gas of cat head enter the superfractionation system, tell the butene-1 of polymerization-grade; The thick polyisobutene of tower still obtains the polyisobutene product through steps such as atmospheric and vacuum distillation, filtrations.
3, according to claim 1 or 2 described from C
4The method of separating butane-1 in the cut is characterized in that the weight of the initiator that adds is mixed C
4The 0.1%-1% of cut.
4, described according to claim 2 from C
4The method of separating butane-1 in the cut is characterized in that described alkali lye is that concentration is the NaOH solution of 10%-30%.
5, according to claim 1 or 2 described from C
4The method of separating butane-1 in the cut is characterized in that used mixed C
4Cut is the light C of catalytic cracking
4Raw material or cracking C
4Raffinate.
6, according to claim 1 or 2 described from C
4The method of separating butane-1 in the cut is characterized in that temperature of reaction is-35～40 ℃.
7, described according to claim 7 from C
4The method of separating butane-1 in the cut is characterized in that polyisobutene molecular weight that described reaction generates 10000 when following, and temperature of reaction is controlled at-10～40 ℃.
8, described according to claim 7 from C
4The method of separating butane-1 in the cut, the polyisobutene molecular weight that it is characterized in that described reaction generation was at 10000～60000 o'clock, and temperature of reaction is controlled at-35～-10 ℃.
9, according to claim 1 or 2 described from C
4The method of separating butane-1 in the cut is characterized in that the described reaction times is 30～180 minutes.
10, according to claim 1 or 2 described from C
4The method of separating butane-1 in the cut is characterized in that described reaction pressure is 0～0.5MPa.
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103508830B (en) * | 2012-06-15 | 2015-05-13 | 中国石油化工股份有限公司 | Method for separating alkanes and olefin in etherification C4 fractions |
| CN107879874B (en) * | 2016-09-30 | 2020-10-23 | 中国石油化工股份有限公司 | Method and device for producing n-butane by mixing C4 |
| CN107879883B (en) * | 2016-09-30 | 2020-09-15 | 中国石油化工股份有限公司 | Method and device for producing butane by mixing C4 |
| CN107879882B (en) * | 2016-09-30 | 2020-09-15 | 中国石油化工股份有限公司 | Method and device for producing normal butane, isobutane and 2-butene by mixing C4 |
| CN109096035A (en) * | 2018-07-17 | 2018-12-28 | 天津大学 | Utilize the method and apparatus of kinetics differential separation alkane and alkene |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103538A (en) * | 1987-05-16 | 1987-11-18 | 中国石油化工总公司大庆石油化工总厂 | A kind of novel aluminum chloride System Catalyst of producing polyisobutene and preparation method thereof that is used to |
| CN1361756A (en) * | 1999-07-16 | 2002-07-31 | 催化蒸馏技术公司 | Process for the separation of isobutene from normal butenes |
| CN1433390A (en) * | 1999-12-23 | 2003-07-30 | 埃克森美孚化学专利公司 | Process for selective dimerisation of isobutene |
| CN1480437A (en) * | 2002-08-06 | 2004-03-10 | �¿�ɭŵ���շһ�ѧ�ɷ�����˾ | Method of low polymerizing isobutene in hydrocarbon stream contg n-butene |
| CN1170858C (en) * | 2000-11-03 | 2004-10-13 | 中国石油天然气股份有限公司 | Process for preparing low-molecular polyisobutylene |
-
2006
- 2006-12-26 CN CNB2006101615738A patent/CN100430353C/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87103538A (en) * | 1987-05-16 | 1987-11-18 | 中国石油化工总公司大庆石油化工总厂 | A kind of novel aluminum chloride System Catalyst of producing polyisobutene and preparation method thereof that is used to |
| CN1361756A (en) * | 1999-07-16 | 2002-07-31 | 催化蒸馏技术公司 | Process for the separation of isobutene from normal butenes |
| CN1433390A (en) * | 1999-12-23 | 2003-07-30 | 埃克森美孚化学专利公司 | Process for selective dimerisation of isobutene |
| CN1170858C (en) * | 2000-11-03 | 2004-10-13 | 中国石油天然气股份有限公司 | Process for preparing low-molecular polyisobutylene |
| CN1480437A (en) * | 2002-08-06 | 2004-03-10 | �¿�ɭŵ���շһ�ѧ�ɷ�����˾ | Method of low polymerizing isobutene in hydrocarbon stream contg n-butene |
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