CN103265393A - Separation method for oligomerization products of 1,3-butadiene ring - Google Patents
Separation method for oligomerization products of 1,3-butadiene ring Download PDFInfo
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- CN103265393A CN103265393A CN201310132648XA CN201310132648A CN103265393A CN 103265393 A CN103265393 A CN 103265393A CN 201310132648X A CN201310132648X A CN 201310132648XA CN 201310132648 A CN201310132648 A CN 201310132648A CN 103265393 A CN103265393 A CN 103265393A
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Abstract
The invention brings forward a separation method for oligomerization products of 1,3-butadiene ring. The method comprises steps of adding an extractant into residues, distilling, fractionating distillate, cooling and settling residual oily substances, and filtering and separating crystal substances, so that an oil liquid of C16-C32 isomer substances, petroleum ether and a 2-butanone mixed solvent extractant are separated from residue distillation ingredients generated in a synthesis of cyclododecatriene, thereby obtaining 1,3-butadiene, cyclododecatriene, cyclooctadiene and vinyl cyclohexene substances. According to the invention, the method can separate the oligomerization products of the 1,3-butadiene ring, and obtain useful substances used for reusing or receiving valuable compounds, thereby reducing discharge, eliminating pollution, protecting the environment, and conserving resources, and being suitable as a method for processing the oligomerization products of the 1,3-butadiene ring.
Description
Technical field
The present invention relates to a kind of separation method of high boiling substance.It particularly is the separation method of the synthetic middle contained component of distillation leftover that produces of cyclododecatriene.A kind of separation method of 1,3-butadiene ring oligomerisation reaction product specifically.
Background technology
The industrializing implementation of 1,3-butadiene ring oligomerisation reaction is finished in transistion metal compound or transition metal complex salt usually.Catalyzer uses normally transistion metal compound and alkyl metal halide, is preferably TiX
4And AlR
yZ
Y-3Being one group specifically makes up.Wherein X independently equals F, Cl, and Br, I, Z are a kind of halogeno-group, R is alkyl, 0＜y≤3.According to different catalyst systems, also must add at least a organic compound or the alkyl sulfoxide compound that contains the 5th main group element in the periodic table of chemical element.The principal product of reaction is cyclododecatriene.Under catalytic condition, the selectivity height of this reaction.Generally, major product cyclododecatriene selectivity can be greater than 92%, cyclododecatriene purity＞99% after making with extra care, and the transformation efficiency of divinyl can reach 98%.
After polyreaction is finished, must carry out refinement treatment to reaction product.At first be to decompose and separate the homogeneous phase complex catalyst.The decomposition catalyst typical method: adopt the 5%-10%NaOH aqueous solution to carry out inactivation reaction, the add-on of the NaOH aqueous solution is 5～8% of reactant cumulative volume.
Palpus quiescent settling 10-20h discharged the NaOH aqueous solution after inactivation reaction finished from the bottom, recycled after the recovery.Thick product is with purifying by distillation.Cyclododecatriene purity＞99% after the purification turns back to unreacted 1,3-butadiene and solvent in the reactive system simultaneously again, and various dimerization and trimerization product are through distilling also with separated from one another.
The importantly processing of distillation tower bottom residuals.The mixture that comprises divinyl oligopolymer high boiling point monomers and polyhutadiene, and numerous high boiling monomers that clear and definite molecular structure is arranged.Typical high boiling point monomers is for being ring compound by from 16 to 32 structures that carbon atom is formed, and one or more side chains may be arranged.
Wherein several representative high boiling point monomers are:
3-(2-butenyl)-1,5, the 9-cyclododecatriene;
The 3-(3-butenyl)-1,5,9-cyclododecatriene;
3-(1-methylpropenyl)-1,5, the 9-cyclododecatriene.
These big ring monomers are many can both be separated in the laboratory test process and clear and definite its structure.Can find at following document in comprehensive detailed description: US 3,658,926 (Butadiene Oligomers and Production Thereof).
The selectivity of big ring product and polyhutadiene is wayward in synthetic.The polyblend that all cyclododecatriene synthetic methods are produced not only comprises cyclododecatriene, cyclooctadiene, vinylcyclohexene, also contains various macrocylc compound and the polyhutadiene that quantity does not wait.And having only cyclododecatriene, cyclooctadiene and vinylcyclohexene have the importance of industrial application.
In cyclododecatriene is optionally synthetic, all can produce a kind of high boiling point and flaxen slightly material residue usually in the constantly accumulation of distillation tower bottom, its total weight range accounts for the 5%-10%(weight percentage of reaction-ure mixture).At normal temperatures, residue is highly viscous liquid, forms solid matter when temperature is lower than-10 ℃.The state of distillation leftover also depends on its composition and temperature.Under reasonable energy expends condition, be unworthy further major product fractionation by distillation from residue being come out.This distillation leftover viscosity is very big in addition, is difficult for packing, stores, and carries.General treatment process is all burned as waste product.And this obviously is not the optimal selection of resource rational utilization, can cause detrimentally affect to ecotope simultaneously yet.The more important thing is, the existence of distillation leftover and constantly accumulation, the disadvantageous effect that the production of cyclododecatriene production equipment is produced is apparent, be necessary to select a kind of economical and effective to handle the method for distillation leftover, to solve the bottleneck problem that influences cyclododecatriene production equipment long period stably manufactured.
Extraction is a kind of effective ways that separate above-mentioned high boiling monomer and polymeric constituent.Relevant patent and document once disclosed the experiment achievement of this respect, as in GB 1 287 252 patents, and the method for implementing described in the example 1: by adding a large amount of acetone (500g), corresponding reaction mixture (162g divinyl-20ml toluene is made solvent).
Yet aspect the synthetic cyclododecatriene of selectivity, it is undesirable to use above-mentioned extracting process effect.Directly acetone is added reaction mixture, come the integral part of precipitation polymers or oligopolymer, separate very insufficient.Owing in the synthetic compound of selectivity, also will extract a large amount of cyclododecatrienes, it is huge to cause on commercial production scale acetone to expend, and cost is too high, does not possess industrialized feasibility.
Therefore be necessary to adopt a kind of the more economical suitable treatment process of distillation leftover to be made it economically, technical have an industrialized feasibility.And all obtain scientific and reasonable application after making above-mentioned each separating substances.The method of the invention will make this purpose be achieved.
Summary of the invention:
In order to isolate useful matter in the distillation leftover that from cyclododecatriene is synthetic, produces, the present invention proposes a kind of separation method of 1,3-butadiene ring oligomerisation reaction residue.This method adds the extraction agent distillation by residue, the distillate cooling-sedimentation, and the filtering separation crystallization separates useful matter from residue.Solve the technical problem of Separation and Recovery useful matter in the 1,3-butadiene ring oligomerisation reaction residue.
1, residue adds the extraction agent distillation: after most major product cyclododecatriene volatile constituents distill in thick product, in the remaining viscous mixture in distillation tower bottom is residual, add mixed extractant, distillate and residue oily matter are obtained in the reflux extraction.
2, distillate fractionation: distillate is joined in the distillation tower, carry out vacuum fractionation, obtain extraction agent, C respectively
16-C
32The oily liquid of isomer high boiling substance, remaining cyclododecatriene, cyclooctadiene, vinylcyclohexene.
3, residue oily matter cooling-sedimentation: will remain the oily matter cooling-sedimentation, and make the polyhutadiene crystallization.
4 filtering separation crystallisates: by filtering, from residue oily matter, isolate the polyhutadiene crystallisate.
Positively effect: utilize the inventive method to separate 1,3-butadiene ring oligomerisation reaction product, obtain useful matter, be used for recycling or collect valuable compounds therefrom, thereby stop to pollute, the protection environment economizes on resources.Suit to use as 1,3-butadiene ring oligomerisation reaction product treatment process.
Embodiment
1, residue adds the extraction agent distillation: after most major product cyclododecatriene volatile constituents distill in thick product, in the remaining viscous mixture in distillation tower bottom is residual, add mixed extractant, distillate and residue oily matter are obtained in the reflux extraction.
Mixed extractant is: sherwood oil and 2-butanone mixed solvent.
Extracting operation pressure is 0.02-0.04mpa.
2, distillate fractionation: distillate is joined in the distillation tower, carry out vacuum fractionation, obtain extraction agent, C respectively
16-C
32The oily liquid of isomer high boiling substance, remaining cyclododecatriene, cyclooctadiene, vinylcyclohexene.
Vacuum fractionation pressure is :-0.098mpa--0.09mpa.
3, residue oily matter cooling-sedimentation: will remain the oily matter cooling-sedimentation, and make the polyhutadiene crystallization.
Settling time is 10-20h.
4 filtering separation crystallisates: by filtering, from residue oily matter, isolate the polyhutadiene crystallisate.
Filtration temperature is 0 ℃-20 ℃.
Specify
Result of study shows, the extraction of distillation leftover: depend on the selected solvent of extraction to the extraction selectivity of each material in the distillation leftover.Evidence non-polar solvent such as unbranched or the side chain aliphatic hydrocarbon arranged, 5 to 8 carbon atoms are preferably arranged, as pentane, hexane, octane, some are polarity ground a little, as contain 3 to 8 carbon atoms and branch is arranged or do not have branch's aliphatic ketone and their mixture all has certain extraction selectivity for each material in the distillation leftover.And being masked as of the best effect of extraction can be come out polyhutadiene extracting and separating in the distillation leftover as much as possible, and crystallized into solid matter, and other materials are wanted as much as possible staying in the extraction liquids.Preferred mixed solvent is selected from: sherwood oil (60-90 ℃) and 2-butanone.
In ring oligomerisation 1,3-butadiene, technology of the present invention is:
At first volatile constituent is separated, at the top of distillation tower major product is separated from high boiling component.The bottom of distillation tower is a kind of mixture of high boiling point thickness, can not reasonably further distill under the cost.Use a kind of extraction solvent according to the present invention or the hybrid extraction solvent comes the extractive distillation residue.
Concrete grammar is to adopt the high temperature reflux method.The surplus heat of distillation tower bottom can be used for the heating extraction agent.After absorbing and cooling off, separate insoluble component with centrifugation method by filtration.
The solvent or the solvent mixture that are used for extraction can come out by fractionation by distillation successively by the boiling point order of material, and the extraction agent of recovery is reused in extraction process.
C
16-C
32The liquid of the oiliness of high boiling point materials such as isomer can further be purified by fractionation by distillation, preferred underpressure distillation mode.
Preferred distillation tower pressure is :-0.098mpa--0.09mpa
In said process, the settling time of extraction mixture and temperature have material impact to the crystallization of polyhutadiene, and cooling extraction mixture can make crystallization increase.And lysed polyhutadiene can further reduce in the extraction liquid.The throw out that obtains mainly is the polymkeric substance of 1,3-butadiene, particularly is polyhutadiene.The also crystallization that it is normally colourless.When selecting suitable extraction agent and temperature, it no longer is thick, therefore can be easy to separate from the extraction mixture, for example adopts suction filter or whizzer.When cooling extraction mixture, the selection of the scope of lowest temperature causes following problem: the solubility that is dissolved in the high boiling point monomers in the extraction agent is too low; Or in contrast, high boiling point monomers is freeze-outed from mixture.In both cases, mixture becomes milky white muddy shape in the extraction step, and makes precipitation bonding.
The preferred settling time is 10-20h, and filtration temperature is 0 ℃-20 ℃.
Boiling point and the working pressure of slective extraction solvent have material impact to effect of extracting, 30 ℃-135 ℃ of the boiling points of slective extraction solvent.Extraction also can be operated under pressurized conditions.Be higher than at solvent boiling point under 115 ℃ the situation, extraction solvent is increased the extraction rate of polyhutadiene, be conducive to the polyhutadiene crystallization.
Preferred extracting operation pressure is 0.02-0.04mpa, is lower than at the boiling point of solvent under 35 ℃ the situation, and the boiling point of extraction agent is just too near the lower limit of the temperature of high boiling point monomers solubility.Should adopt the excellent performance extraction agent, also can be in conjunction with the extraction agent that adopts two or more.
As the further related process of the present invention: the residue of the major product that does not come out by fractionation by distillation, can extract by extraction from the distillation tower bottom.By this method, can extract the major product of residue ring oligomerisation reaction in the residue, as: cyclododecatriene, cyclooctadiene, vinylcyclohexene.
The potential Application Areas of these high boiling point monomers comprises medicine, perfume and spices industry, for example, and synthetic (3,865,888, the Process for Producing Cycloalkenes) of macrocyclic ketone class.And these compounds are mainly used in the linking agent in the synthetic rubber, for example, and tire; The multipolymer of plastic prod and oil paint additive etc.（US20040260129A1,?6(2,7-Octadienyl）1,4-Cyclooctadiene)。
The extraction example:
In the following Example, getting residue after the distillation of preparation cyclododecatriene, join in the extraction agent of 300ml, is 115 ℃ in temperature, and pressure is reflux extraction 45 minutes under the condition of 0.01mpa.Mixture is cooled to 5 ℃ or 20 ℃ subsequently, static sedimentation down 12 hours, subsequent filtration.Filtrate is extraction agent and high boiling substance, and filter cake is polyhutadiene, the weight of weighing filtrate and filter cake.Because the small amount of residual thing adheres to experimental installation, causes the initial sum final weight variant.
The distillation example:
Obtaining 205 g filtrates and place the 500ml matrass in the extraction example, is 1.5m by a height under underpressure distillation, and internal diameter is the rectifying tower of 0.05m.Under differing temps and pressure, isolate following material.
The rectifying product:
Solvent: weight 90g, 110 ℃ of temperature, pressure 0.02mpa, purity 98%, water white oil;
Cyclododecatriene: weight 4.2 g, 150 ℃ of temperature, pressure-0.09 mpa, purity 99%, water white oil,
C
16: weight 80.5 g, 170 ℃ of temperature, pressure-0.098mpa, purity 90%, water white oil;
C
20-C
32: weight 11.1 g, 200 ℃ of temperature, pressure-0.099 mpa, faint yellow oily thing;
Residue: 5g, the oil of black.
Product recovery rate:＞85%, solvent recovering rate:＞90%.
Infrared spectroscopy C
16-32The part proof: 3-(3-butenyl) 1,5,9-cyclododecatriene are main component.
Extraction test:
Index is successively in order: extraction agent boiling point ℃, and residue weight g, filtration temperature ℃, filtrate weight g, precipitation weight g, the filtrate form, the precipitation form is respectively:
The n-normal heptane: 98 ℃, 159.2 grams, 20 ℃, 129.3 grams, 21.4 grams, faint yellow oily thing, colourless toughness;
Sherwood oil: 60～90,175.8,20,159.1,10.3, yellow oil, colourless powdery;
Sherwood oil: 60～90,152.2,5,84.2,55.1, yellow oil, colourless toughness;
Acetone: 56,139.2,20,76.6,53.5, yellow oil, colourless toughness;
2-butanone: 79,171.4,20,146.1,13.2, yellow oil, colourless powdery;
2-butanone: 79,131.6,5,105.1,18.2, yellow oil, colourless powdery.
Claims (5)
1. the separation method of a 1,3-butadiene ring oligomerisation reaction product is characterized in that: separate substance in the distillation residual component that from cyclododecatriene is synthetic, produces, and it is as follows to pass through step:
1), residue adds the extraction agent distillation: after most major product cyclododecatriene volatile constituents distill in thick product, in the remaining viscous mixture in distillation tower bottom is residual, add mixed extractant, distillate and residue oily matter are obtained in the reflux extraction;
2), distillate fractionation: distillate is joined in the distillation tower, carry out vacuum fractionation, obtain extraction agent, C respectively
16-C
32The oily liquid of isomer high boiling substance, remaining cyclododecatriene, cyclooctadiene, vinylcyclohexene;
3), residue oily matter cooling-sedimentation: will remain the oily matter cooling-sedimentation, and make the polyhutadiene crystallization;
4), filtering separation crystallisate: by filtering, from residue oily matter, isolate the polyhutadiene crystallisate.
2. the separation method of a kind of 1,3-butadiene ring oligomerisation reaction product according to claim 1, it is characterized in that: employed mixed extractant is in the step 1: sherwood oil and 2-butanone mixed solvent; Extracting operation pressure is 0.02-0.04mpa.
3. the separation method of a kind of 1,3-butadiene ring oligomerisation reaction product according to claim 1, it is characterized in that: the vacuum fractionation pressure of step 2 is :-0.098mpa--0.09mpa.
4. the separation method of a kind of 1,3-butadiene ring oligomerisation reaction product according to claim 1, it is characterized in that: the settling time of step 3 is 10-20h.
5. the separation method of a kind of 1,3-butadiene ring oligomerisation reaction product according to claim 1, it is characterized in that: the filtration temperature in the step 4 is 0 ℃-20 ℃.
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Application publication date: 20130828 |