CN1138795C - Process for the preparation of polybutene - Google Patents
Process for the preparation of polybutene Download PDFInfo
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- CN1138795C CN1138795C CNB951047469A CN95104746A CN1138795C CN 1138795 C CN1138795 C CN 1138795C CN B951047469 A CNB951047469 A CN B951047469A CN 95104746 A CN95104746 A CN 95104746A CN 1138795 C CN1138795 C CN 1138795C
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Abstract
A method to prepare polybutene from C4 hydrocarbon materials comprises: under the condition of keeping the mol ratio of the isobutene in a reactor and the butadiene in the material at 4:1 or higher, and the mol ratio of the isobutene in the reactor and the n-butene in the material at 1:15 or higher, the C4 hydrocarbon is polymerized with the fluro-catalyst whose volume is 0.05-0.5 percent weight of the isobutene in the material under the temperature of -40 to 50 Celsius system and the pressure of 1-10 ; a first alkaline solution is used to neutralize the polymerization in the polymerisate containing the catalyst and adjust the PH value of the generated solution to be kept between 8 and 12 to eliminate the great mass of the catalyst in the resultant of reaction; a second alkaline solution is used to extract the remains of the catalyst in the neutralization resultant and adjust the PH value of the generated solution to be 12 or higher; the process water is used to wash the resultant to get rid of the alkaline components.
Description
The present invention relates to a kind of superperformance that has, for example have the preparation method of the polybutene of high viscosity index (HVI), particularly relate to heavy oil catalytic cracking process of using from refining of petroleum or the C that from the petroleum naphtha cracking process, obtains
4Iso-butylene in the hydro carbons carries out the method that selective polymerisation prepares polybutene.
The polybutene that belongs to liquid polymer is by the C that contains iso-butylene, divinyl, n-butene, butane etc.
4Hydrocarbon mixture carries out cationic polymerization and obtains.These polybutene are colourless, tasteless, nontoxic, thickness and gluing material, thereby can extensively be used as tackiness agent, lubricating oil thickening material, transformer oil, sealing agent, caulking agent, softening agent, asphalt modifier agent and dispersion agent, particularly be used as lubricating oil and lubricating oil additive.
As everyone knows, polybutene can make C by using a kind of Friedel-Crafts catalyst in-20 ℃ to 30 ℃ temperature range
4Hydro carbons carries out polymerization and separates remaining catalyzer then from product and prepare described C
4Hydro carbons is from different raw material production, and these raw materials for example are the raw materials that the heavy oil fluid catalytic cracking from refining of petroleum is come, or the C from the petroleum naphtha cracking
4Hydrocarbon mixture carries out the raw material that the 1,3-butadiene extracting obtains.
USP3 has described a kind of method that improves the polybutene productive rate in 121,125, and this method has been used a kind of catalyzer from the big consumption of 0.5-1.5% (weight) scope with respect to alkene weight.Yet the weak point of this method is that the isobutylene concentration in reaction system is lower, has increased the side reaction of n-butene such as butene-1, butene-2 etc. thus, and has reduced the viscosity index of desirable product.The polybutene that obtains has in view of the above limited its application as lubricating oil medium viscosity index toughener.In addition, the divinyl that may contain in the reaction monomers is easy to participate in this reaction, and influences the smell and/or the color of final product.In order to address these problems, advise among the open 93-6910 of Korean Patent that the side reaction of divinyl can be by adding a kind of C
4LPG adds component or makes raw material not contain divinyl by partial hydrogenation as a kind of in the raw material reduces the side reaction of divinyl, thereby prevents that product performance from reducing.
In addition, when the amount of catalyst system therefor was very big, the catalyzer that must will stay after reaction in the product reclaimed so that re-use by a settling vessel.In this removal process, the back will take place in settling vessel to answer, this will make C
4-C
24The growing amount of oligopolymer increases, and the molecular weight distribution of product is broadened.
Remove the chemical method that the traditional method of staying the catalyzer in the product after polyreaction is finished comprises physics method (as deposition, filtration and absorption) and makes water, ammonia and alkaline solution (as ammoniacal liquor, sodium hydroxide and potassium hydroxide).At this on the one hand, USP2,677, the method that removes residual catalyst by successive sedimentation in settling vessel has been described in 002, but the shortcoming of this method is to have lost unreacted gas and be included in polymkeric substance in the catalyzer of this removal, and since in settling vessel the generation afterreaction make C
8-C
24The growing amount of oligopolymer increases.In addition; Because this deposition method can not be removed residual catalyzer effectively from the gained butene polymers, also need process such as handling with additional steps such as activated clay absorption, filtration or chemical methods.The defective of absorption and filter method is to carry out in a continuous manner, and depleted clay and the catalyzer of getting rid of can become environmental hazard, and the cost of this process is higher.In addition, also afterreaction may take place, thereby generate oligopolymer and the molecular weight distribution of product is broadened in absorption and filtration procedure.
Described the chemical process that the catalyzer in the reaction system is stayed in a kind of removal among special public (clear) 60-124603 of Japanese Patent, this method is with reaction product difference water, alkaline solution, water thorough washing.But this method requires the equipment of the costliness made with antiacid corrosion material, because the generation of HCl gas is arranged in washing process.USP3,121, a kind of method of removing catalyzer has been described in 125, this method is to form solid ammonia-aluminum chloride mixture with ammonia, then by deposition, filtration or centrifugal it is separated with reaction product, but ammonia may still be stayed in unreacted gas or the product, and stays the C of the end reaction in the isolating mixture
4The amount of mixture and polymerisate is 10 times of ammonia-aluminum chloride mixture amount.
Among Japanese Patent (clear) the 60-48526 B2 a kind of method of removing residual catalyst has been described.This method is to be that half or more a kind of alkaline aqueous solution of reaction product volume contacts with reaction product with consumption, and the pH value of the solution after the contact is remained more than 10 or 10.But, in this case, owing to can generate the catalyst residue of emulsion-type in reaction product and alkaline solution contact process, it is separated not exclusively, thereby make residual catalyst may change into oxyhydroxide and be incorporated in the product, the color of the finished product and electrical properties are degenerated.
Based on the result of study that addresses these problems, the present inventor finds that from the reactive behavior of reaction monomers, the activity of iso-butylene is than divinyl or n-butene height; The butadiene content height can cause the color burn of product in the reaction monomers, and n-butene content height can cause the viscosity index of product to reduce in the reaction monomers.In addition, the inventor also finds when making by the catalytic amount of control in the reaction system that the ratio of iso-butylene and divinyl and n-butene remains in the given scope in the reaction monomers, even contain divinyl in the reaction monomers, the reaction of divinyl and n-butene also can be inhibited, thereby makes final product have relative higher viscosity index compared with the prior art.
In addition, the inventor also finds, in the continuous purification process after polymerization, the alkaline aqueous solution that is 8-12 with a kind of pH value when the reaction product that contains catalyzer neutralizes, when also washing greater than 12 alkaline aqueous solution extracting with water of productive use capable of circulation with a kind of pH value, the wastewater flow rate that this process produces can significantly reduce, and the effect of removal catalyzer is strengthened.
Therefore, a main purpose of the present invention provides a kind of C from obtaining such as heavy oil fluid catalytic cracking or petroleum naphtha cracking method
4Hydro carbons prepares and has the method for superperformance as polybutene with high viscosity index (HVI).
According to one aspect of the present invention, the invention provides a kind of from containing the C of iso-butylene, divinyl and n-butene
4Hydrocarbon raw material prepares the method for polybutene, and this method comprises:
(a) iso-butylene in keeping reactor and the mol ratio of the divinyl in the said raw material are 4: 1 or higher, and with the mol ratio of n-butene in the said raw material be under 1: 15 or the higher situation, with C
4Hydro carbons carries out polymerization in-40 to 50 ℃ temperature ranges and 1 to 10 atmospheric pressure range in the presence of consumption is a kind of Friedel-Crafts catalyst with respect to the 0.05-0.5% (weight) of the iso-butylene weight in the said raw material;
(b) contain the polymerisate of catalyzer with first alkaline aqueous solution neutralization, the pH value of adjusting gained solution simultaneously is in the scope of 8-12, to remove most catalyzer in the reaction product;
(c) go out to be included in the lingering section of the catalyzer in the product after the neutralization with the second alkaline aqueous solution extracting, the pH value of adjusting gained solution simultaneously is 12 or higher; And
(d) wash products therefrom to remove basic component with water of productive use.
Brief Description Of Drawings:
Fig. 1 is a schematic flow sheet of describing polybutene preparation method of the present invention.
Preparation polybutene used hydrocarbon raw material comprises the C that obtains from RFCC or naphtha cracking among the present invention4Hydro carbons. The composition of hydrocarbon raw material can be among the present invention: the butane of 5-25% (mole), the butene-1 of 5-30% (mole), the trans-butene-2 of 5-15% (mole), the cis-butene-2 of 2-8% (mole), the butadiene of the isobutene of 15-60% (moles) and 0.01-5% (mole).
According to the present invention, the polymerisation of hydrocarbon raw material is to be-4 0 ℃ to 50 ℃ in temperature, and preferably-20 ℃ to 40 ℃, pressure is to carry out under 1 to 10 atmospheric condition. If reaction pressure is higher than 10 atmospheric pressure, the design of device needs strictly withstand voltage.
In the method for the invention, said the first alkaline aqueous solution is the solution that can reclaim from said step (c), and said the second alkaline aqueous solution can be the solution that alkaline aqueous solution that the water that reclaims from said step (d) and a kind of concentration are the 1-50 % by weight mixes.
The catalyst that can use in the present invention comprises lewis acid catalyst; In these catalyst, Friedel-Crafts catalyst more preferably, and aluminium chloride most preferably.
According to the present invention, the amount ranges of employed catalyst is the 0.05-0.5 % by weight with respect to the isobutene weight in the raw material in reaction system, and therefore so that in the technical process in the isobutene in the reaction system and the raw material mol ratio of n-butene and butadiene be respectively 1/15 or higher and 4 or higher. Under such condition, even there is a large amount of butadiene, the side reaction of butadiene also can be suppressed, so just can remove the preprocessing process (for example hydrogenation) of butadiene.
After this be that polymerizate is carried out purifying, this purifying comprises neutralization, extracting and washing step: neutralization procedure is that the product that will contain catalyst contacts with the first alkaline aqueous solution, adjust the pH value of gained solution in the scope of 8-12, to remove the most of catalyst in the product; Extraction steps is that product is contacted with the second alkaline aqueous solution again, and the pH value of adjusting gained solution is 12 or higher, to remove catalyst residual in the product; Washing step is not contain the product industrial water of catalyst, and for example the water of adsorption and purification or distilled water wash to remove wherein residual basic component. In this technical process, the industrial water that reclaims from washing step can circulate and turn back to extraction steps, and then circulation turns back to neutralization procedure. In other words, the first alkaline solution that is used for neutralization procedure also can be the solution that comes from extraction steps, and the second alkaline solution that is used for extraction steps also can be the solution that comes from washing step. Such cyclic process has strengthened removes the efficient of catalyst, and reduces to greatest extent the quantity of wastewater effluent of product purification system.
Can be used for the aqueous solution that alkaline aqueous solution of the present invention comprises sodium hydroxide, potassium hydroxide and calcium hydroxide, wherein sodium hydroxide is most preferred.
A kind of embodiment preferred of the inventive method as shown in Figure 1.According to Fig. 1, C
4Hydro carbons and add the reactor 12 from the Friedel-Crafts catalyst that catalyzer basin 11 provides, under the iso-butylene in the reactor that keeps as previously described and the corresponding mol ratio of divinyl in the raw material and n-butene and the condition with respect to the catalyst levels of the iso-butylene in the raw material, polymerization reaction take place in reactor.The reaction product that contains catalyzer enters first mixing tank 21, reaction product contacts to be neutralized and to make wherein contained catalyst deactivation with first alkaline aqueous solution in mixing tank 21, then this mixture is moved into first settling vessel 22, the most of catalyzer in the reaction product is discharged from the lower region of settling vessel 22.The reaction product that contains the catalyst residue that exists with form of emulsion in the upper area of settling vessel 22 enters second mixing tank 23, reaction product contacts with second alkaline aqueous solution in mixing tank 23, then mixture is moved into second settling vessel 24, in this settling vessel with reaction product in residual catalyzer discharge from lower region thereof.The reaction product that does not contain catalyzer in settling vessel 24 upper areas enters the 3rd mixing tank 25, and reaction product to remove alkaline components residual in the reaction product, moves into mixture the 3rd settling vessel 26 with purified water or distilled water wash then in mixing tank 25.Water of productive use partly circulated turns back to the 3rd mixing tank 25, and rest part and consumption are that three times of catalyzer molar weight residual in the reaction product or alkaline aqueous solution more, that concentration is 1-50% (weight) mix, and circulation enters second mixing tank 23 then.After this, the part circulation of the water of productive use that reclaims from second settling vessel, 24 lower regions enters second mixing tank 23, and the rest part circulation enters first mixing tank 21, discharges from the lower region of first settling vessel 22 then.
First, second, third used mixing tank is the stirring-type mixing tank or used filter sand or fixed mixing tank that Ceramic Balls is filled among the present invention, be used to make reaction mass to mix and make emulsion breakdown, its can be separately or, preferably be used in combination.First, second, third settling vessel generally is to be used for mixture by leaving standstill the device that is divided into water and organic phase.
In first mixing tank 21, contact and be neutralized to the pH value with the alkaline aqueous solution that reclaims from second settling vessel, 24 lower regions from the reaction product of reactor 12 is 8-12, makes the catalyst deactivation in the reaction product and is removed.
In second mixing tank 23, contact with the water of productive use that reclaims from the 3rd settling vessel lower region and mix from the reaction product of first settling vessel 22, to remove residual catalyzer or any acidic components fully with the alkaline aqueous solution of 1-50% (weight).The amount of said alkaline aqueous solution neutral and alkali composition is to enter three times of the contained catalyzer mole number of reaction product in first mixing tank 21 or more, if catalyzer or acidic components are not removed fully, then the thermostability of the finished product reduces, in the oligopolymer recycling step when temperature reach 150 ℃ or when higher their variable color degree increase, quality product will suffer damage in procedure of processing subsequently.The pH value that enters the alkaline solution of second mixing tank preferably is adjusted into 12 or higher, and the excessive use of alkaline solution will increase production cost and wastewater flow rate.
In the 3rd mixing tank 25, reaction product water of productive use from second settling vessel 24, wash removing alkaline components residual in the reaction product as adsorption and purification water or distilled water, thereby prevent from the electric property of the finished product to be reduced owing to the existence of sodium, calcium, potassium etc.
Reaction product through above-mentioned purifying enters C
4Distillation tower 31 is to separate unreacted C
4Raw material enters an atmospheric distillation tower 32 and a vacuum still 33 then so that separate C effectively from final polybutene product
8-C
24Oligopolymer.
The following examples will illustrate the present invention more fully but not limit protection scope of the present invention.
Embodiment 1
With a kind of C
4Hydrocarbon raw material adds in the ring-like reactor 12 with about 60 kilograms/hour amount, have aluminum chloride to exist and 10 ℃, 3 atmospheric conditions under carry out polymerization, this C
4Hydrocarbon raw material is the C that generates from the petroleum naphtha cracking
4Hydrocarbon mixture obtains after removing divinyl, it consists of: the iso-butylene of 42.0% (mole), the Trimethylmethane of 3.0% (mole), the normal butane of 9.0% (mole), the 1,3-butadiene of 1.0% (mole), 0.2% (mole) 1, the 2-divinyl, the butene-1 of 31.0% (mole), the suitable-butene-2 of the anti--butene-2 and 4.3% (mole) of 9.5% (mole).Amount by control aluminum chloride be about 0.25% (weight) (about 63 Grams Per Hours) with respect to the iso-butylene weight in the raw material, thereby the concentration of iso-butylene is about 5.0% (mole) in the maintenance reactor.Products therefrom is carried out purifying through a series of mixing tanks and settling vessel shown in Figure 1, the amount of wherein adding the water of productive use in the 3rd mixing tank 25 remains 1/3 (30 liters/hour) of reaction product volume, and the sodium hydroxide solution of 20% (weight) is mixed resulting 0.3% (weight) in back with the water of productive use that reclaims from the 3rd settling vessel 26 lower regions alkaline aqueous solution circulates and turns back to second mixing tank 23.The reaction product that will not contain catalyzer then feeds a series of distillation towers as shown in Figure 1 to remove unreacted C
4Raw material and C
8-C
24Oligopolymer per hour obtains 22 kilograms polybutene.
The viscosity index and the number-average molecular weight (Mw) of gained polybutene are compared with commerical prod, and the results are shown in Table 1 for it.
Table 1
* Mw calculates according to ASTM D3592.The * viscosity index records according to ASTM D567.
| Product | Mw* | Viscosity index * * |
| Amoco H-300 | 1290 | 117 |
| Amoco H-100 | 920 | 109 |
| Idemitsu 100M | 980 | 130 |
| Embodiment 1 | 1250 | 170 |
Embodiment 2
Repeat the process of embodiment 1, just temperature of reaction remains 25 ℃, the Mw of products obtained therefrom, and viscosity index and colourity are listed in the table 2.
Comparative Examples 1
Repeat the process of embodiment 1, just the add-on of catalyzer changes about 1.0% (weight) (about 252 Grams Per Hours) with respect to iso-butylene weight in the raw material into, and the concentration of iso-butylene remains about 2.0% (mole) in the reactor.The results are shown in Table 2 for gained.
Embodiment 3
With a kind of C
4Hydrocarbon raw material adds in the ring-like reactor 12 with about 60 kilograms/hour amount, have aluminum chloride to exist and 20 ℃, 3 atmospheric conditions under carry out polymerization, this C
4Consisting of of hydrocarbon raw material: the iso-butylene of 42.0% (mole), the Trimethylmethane of 4% (mole), the normal butane of 10.0% (mole), 2.5% (mole) 1, the 3-divinyl, the 1 of 0.5% (mole), the butene-1 of 29.0% (mole), the suitable-butene-2 of the anti--butene-2 and 4% (mole) of 8.0% (mole).Amount by control aluminum chloride be about 0.14% (weight) (about 36 Grams Per Hours) with respect to iso-butylene weight in the raw material, thereby the concentration of iso-butylene is about 12% (mole) in the maintenance reactor.Then, products therefrom is carried out purifying according to the same way as among the embodiment 1, per hour obtain 20 kilograms polybutene.The results are shown in Table 2 for it.
Comparative Examples 2
Repeat the process of embodiment 3, just the add-on of catalyzer is changed into about 1.0% (weight) (about 252 Grams Per Hours), and the concentration of iso-butylene is about 2.0% (mole) in the maintenance reactor with respect to iso-butylene weight in the raw material.The results are shown in Table 2 for it.
Embodiment 4
With a kind of C
4Hydrocarbon raw material adds in the ring-like reactor 12 with about 60 kilograms/hour amount, is having aluminum chloride to exist and carry out polymerization, this C under-3 ℃, 3 atmospheric conditions
4Consisting of of hydrocarbon raw material: the iso-butylene of 30.0% (mole), the Trimethylmethane of 5.0% (mole), the normal butane of 10.0% (mole), 1.6% (mole) 1, the 3-divinyl, the 1 of 0.4% (mole), the butene-1 of 38.0% (mole), the suitable-butene-2 of the anti--butene-2 and 4.5% (mole) of 10.5% (mole).Amount by control aluminum chloride be with respect to you of iso-butylene weight in the raw material) instead-suitable-butene-2 of butene-2 and 4.5% (mole).Amount by control aluminum chloride be about 0.17% (weight) (about 30 Grams Per Hours) with respect to iso-butylene weight in the raw material, thereby the concentration of iso-butylene is about 8% (mole) in the maintenance reactor.Then, products therefrom is carried out purifying according to mode identical among the embodiment 1, per hour obtain 15 kilograms polybutene.The results are shown in Table 2 for it.
Comparative Examples 3
Repeat the process of embodiment 4, just the add-on of catalyzer is changed into about 1.0% (weight) (about 180 Grams Per Hours), and the concentration of iso-butylene is about 2.0% (weight) in the maintenance reactor with respect to iso-butylene weight in the raw material.The results are shown in Table 2 for it.
Embodiment 5
Will be by 46.5% (mole) iso-butylene, 3.0% (mole) Trimethylmethane, 9.0% (mole) normal butane, 2.9% (mole) 1,3-butadiene, 0.6% (mole) 1, the 2-divinyl, 26.0% (mole) butene-1,8% (mole) be anti--butene-2 and 4% (mole) is suitable-C of butene-2 composition
4Hydrocarbon raw material adds in the ring-like reactor 12 with about 60 kilograms/hour amount, is having aluminum chloride to exist and carry out polymerization under 30 ℃, 4 atmospheric conditions.Amount by control aluminum chloride be about 0.11% (weight) (about 31 Grams Per Hours) with respect to iso-butylene weight in the raw material, thereby the concentration of iso-butylene is about 25% (mole) in the maintenance reactor.Then, products therefrom is carried out purifying according to mode identical among the embodiment 1, per hour obtain about 16.5 kilograms polybutene.The results are shown in Table 2 for it.
Comparative Examples 4
Repeat the process of embodiment 5, just the add-on of catalyzer is changed into about 0.17% (weight) (about 46.5 Grams Per Hours), and the concentration of iso-butylene is about 8.0% (mole) in the maintenance reactor with respect to iso-butylene weight in the raw material.The results are shown in Table 2 for it.
Comparative Examples 5
Repeat the process of embodiment 5, just the add-on of catalyzer is changed into about 1.0% (weight) (about 279 Grams Per Hours), and the concentration of iso-butylene is about 2.0% (mole) in the maintenance reactor with respect to iso-butylene weight in the raw material.The results are shown in Table 2 for it.
Table 2
* Mw calculates according to ASTM D3592.* viscosity is dragged number and is recorded according to ASTM D567.* * colourity (APHA) records according to ASTM D1209.
| Temperature (℃) | The mol ratio of iso-butylene and divinyl | The mol ratio of iso-butylene and n-butene | Mw * | Viscosity index * * | Colourity (APHA) * * * | ||
| Embodiment | 1 | 10 | 5∶1.2 | 5∶44.8 | 1250 | 170 | 20 |
| 2 | 25 | 5∶1.2 | 5∶44.8 | 720 | 140 | 20 | |
| 3 | 20 | 12∶3 | 12∶41 | 1460 | 180 | 20 | |
| 4 | -3 | 8∶2 | 8∶53 | 2300 | 200 | 20 | |
| 5 | 30 | 25∶3 | 25∶38 | 1260 | 220 | 20 | |
| Comparative Examples | 1 | 10 | 2∶1.2 | 2∶48.8 | 900 | 95 | 70 |
| 2 | 20 | 2∶3 | 2∶41 | 620 | 90 | 120 | |
| 3 | -3 | 2∶2 | 2∶53 | 1900 | 150 | 150 | |
| 4 | 30 | 8∶3 | 8∶38 | 820 | 160 | 50 | |
| 5 | 30 | 2∶3 | 2∶38 | 450 | 80 | 150 | |
Embodiment 6
The reaction product that contains catalyzer that 90 liters/hour embodiment 1 obtain is carried out purifying according to mode identical among the embodiment 1, different is that about 40 liters/hour water of productive use is added in the 3rd mixing tank 25, and the alkaline aqueous solution circulation of 0.3% (weight) that mix of the sodium hydroxide solution of the water of productive use and 20% (weight) that will be retrieved by the lower region of the 3rd settling vessel 26 turns back in second mixing tank 23.Last nearly 40 liters/hour pH is that total waste water of 9.5 is discharged from the bottom section of first settling vessel 22.Polybutene behind the gained purifying contains the aluminium of 1ppm.
Comparative Examples 6
The reaction product that contains catalyzer that 90 liters/hour embodiment 1 are obtained with embodiment 6 in the identical mixing tank aqueous sodium hydroxide solution with about 40 liters/hour 0.3% (weight) neutralize and sedimentation in a settling vessel.The reaction product of this settling vessel upper area is washed with about 40 liters/hour water of productive use, and use with embodiment 6 in identical mode handle.In this Comparative Examples, finally produce about 40 liters/hour pH value and be 9.5 alkaline waste water and about 40 liters/hour pH value and be 8.0 waste water.The Mw of gained purifying polybutene, colourity and aluminium content are listed in the table 3.
Embodiment 7
The reaction product that contains catalyzer that 90 liters/hour embodiment 2 are obtained use with embodiment 1 in identical mode carry out purifying, different is that about 25 liters/hour water of productive use is added in the 3rd mixing tank 25, and 0.5% (weight) alkaline aqueous solution circulation that the sodium hydroxide solution of the water of productive use and 20% (weight) that will be retrieved by the 3rd settling vessel 26 bottom sections mixes turns back to second mixing tank 23.Last nearly 25 liters/hour pH value is the lower region discharge from first settling vessel 22 of total waste water of 10.5.The Mw of the polybutene behind the gained purifying, colourity and aluminium content are listed in the table 3.
Comparative Examples 7
The reaction product that contains catalyzer that 90 liters/hour embodiment 2 are obtained with embodiment 7 in the identical mixing tank aqueous sodium hydroxide solution with about 25 liters/hour 0.3% (weight) neutralize and sedimentation in a settling vessel.The reaction product of this settling vessel upper area is washed with about 25 liters/hour water of productive use, and use with embodiment 7 in identical mode handle.In this Comparative Examples, finally produce about 25 liters/hour pH value and be 10.5 alkaline waste water and about 25 liters/hour pH value and be 8.0 waste water.The Mw of gained purifying polybutene, colourity and aluminium content are listed in the table 3.
Embodiment 8
The reaction product that contains catalyzer that 90 liters/hour embodiment 3 are obtained use with embodiment 1 in identical mode carry out purifying, different is that about 30 liters/hour water of productive use is added in the 3rd mixing tank 25, and the alkaline aqueous solution circulation of 0.5% (weight) that mix of the potassium hydroxide solution of the water of productive use and 5% (weight) that will be retrieved by the 3rd settling vessel 26 bottom sections turns back in second mixing tank 23.Last nearly 30 liters/hour pH value is the lower region discharge from first settling vessel 22 of total waste water of 10.5.The Mw of gained purifying polybutene, colourity and aluminium content are listed in the table 3.
Comparative Examples 8
The reaction product that contains catalyzer that 90 liters/hour embodiment 3 are obtained with embodiment 8 in the identical mixing tank aqueous sodium hydroxide solution with about 30 liters/hour 0.5% (weight) neutralize and sedimentation in a settling vessel.The reaction product of this settling vessel upper area is washed with about 30 liters/hour water of productive use, and use with embodiment 8 in identical mode handle.In this Comparative Examples, finally produce about 30 liters/hour pH value and be 10.5 alkaline waste water and about 30 liters/hour pH value and be 8.0 waste water.The Mw of gained purifying polybutene, colourity and aluminium content are listed in the table 3.
Embodiment 9
The reaction product that contains catalyzer that 90 liters/hour embodiment 4 are obtained use with embodiment 1 in identical mode carry out purifying, different is that about 30 liters/hour water of productive use is added in the 3rd mixing tank, and the alkaline aqueous solution circulation of 0.8% (weight) that mix of the potassium hydroxide solution of the water of productive use and 50% (weight) that will be retrieved by the 3rd settling vessel 26 bottom sections turns back in second mixing tank 23.Last nearly 30 liters/hour pH value is the lower region discharge from first settling vessel 22 of total waste water of 11.5.The Mw of gained purifying polybutene, colourity and aluminium content are listed in the table 3.
Comparative Examples 9
The reaction product that contains catalyzer that 90 liters/hour embodiment 4 are obtained with embodiment 7 in the identical mixing tank aqueous sodium hydroxide solution with about 30 liters/hour 0.3% (weight) neutralize and sedimentation in a settling vessel.The reaction product of this settling vessel upper area is washed with about 30 liters/hour water of productive use, and handles by mode identical among the embodiment 9.In this Comparative Examples, finally produce about 30 liters/hour pH value and be 11.5 alkaline waste water and about 30 liters/hour pH value and be 8.0 waste water.The Mw of gained purifying polybutene, colourity and aluminium content are listed in the table 3.
Table 3
| Mw | Colourity (APHA) | Aluminium content (ppm) | Total wastewater flow rate (l/hr) | ||
| Embodiment | 6 | 1250 | 20 | 1 | 40 |
| 7 | 720 | 20 | 1 | 25 | |
| 8 | 1460 | 20 | 1 | 30 | |
| 9 | 2300 | 20 | 2 | 30 | |
| Comparative Examples | 6 | 1250 | 80 | 45 | 80 |
| 7 | 720 | 60 | 25 | 50 | |
| 8 | 1460 | 100 | 60 | 60 | |
| 9 | 2300 | 120 | 80 | 60 | |
More than of the present invention, describe as can be seen, according to the present invention, by the suitable control of catalyst levels, thereby the divinyl in maintenance iso-butylene and the raw material and the mol ratio of n-butene are certain value, can obtain having good character, the polybutene that for example has high viscosity index (HVI) and low colourity.In addition, according to the present invention, catalyzer contained in the reaction product can be removed effectively, can significantly reduce wastewater flow rate by recycling of water of productive use and alkaline aqueous solution simultaneously.
When the present invention is described according to above special embodiment, should be realized that those skilled in the art can make various improvement and change to the present invention in the defined scope of the additional claim of the present invention.
Claims (5)
1, a kind of from containing the C of iso-butylene, divinyl and n-butene
4Hydrocarbon raw material prepares the method for polybutene, and this method comprises:
(a) iso-butylene in keeping reactor and the mol ratio of the divinyl in the said raw material are 4: 1 or higher, and with the mol ratio of n-butene in the said raw material be under 1: 15 or the higher situation, with C
4Hydro carbons carries out polymerization in-40 to 50 ℃ temperature ranges and the atmospheric pressure range of 1-10 in the presence of consumption is a kind of Friedel-Crafts catalyst with respect to the 0.05-0.5 weight % of the iso-butylene weight in the said raw material;
(b) contain the polymerisate of catalyzer with first alkaline aqueous solution neutralization, the pH value of adjusting gained solution simultaneously in the scope of 8-12 to remove most catalyzer in the reaction product;
(c) go out to be included in the lingering section of the catalyzer in the neutralized reaction product with the second alkaline aqueous solution extracting, the pH value of adjusting gained solution simultaneously is 12 or higher;
(d) wash products therefrom to remove basic component with water of productive use.
2, according to the process of claim 1 wherein that said catalyzer is an aluminum chloride.
3, according to the process of claim 1 wherein that said temperature is-20 ℃ to 40 ℃.
4, according to the process of claim 1 wherein said C
4Hydrocarbon raw material contains the butane of 5-25 mole %, the butene-1 of 5-30 mole %, anti--butene-2 of 5-15 mole %, suitable-butene-2 of 2-8 mole %, the divinyl of the iso-butylene of 15-60 mole % and 0.01-5 mole %.
5, according to the method for claim 1, wherein said first alkaline aqueous solution is the solution that reclaims from said step (c), and said second alkaline aqueous solution is the water that reclaims from said step (d) and a kind of concentration is that 1-50 measures the solution that the alkaline aqueous solution of % mixes.
Applications Claiming Priority (6)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR12193/1994 | 1994-05-31 | ||
| KR12194/94 | 1994-05-31 | ||
| KR12193/94 | 1994-05-31 | ||
| KR12194/1994 | 1994-05-31 | ||
| KR1019940012194A KR0152136B1 (en) | 1994-05-31 | 1994-05-31 | The process for the preparation of polybutene |
| KR1019940012193A KR0154363B1 (en) | 1994-05-31 | 1994-05-31 | The process for the preparation of polybutene |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1118355A CN1118355A (en) | 1996-03-13 |
| CN1138795C true CN1138795C (en) | 2004-02-18 |
Family
ID=26630406
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB951047469A Expired - Lifetime CN1138795C (en) | 1994-05-31 | 1995-04-28 | Process for the preparation of polybutene |
Country Status (3)
| Country | Link |
|---|---|
| CN (1) | CN1138795C (en) |
| MY (1) | MY131071A (en) |
| TW (1) | TW316267B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6858188B2 (en) * | 2003-05-09 | 2005-02-22 | Texas Petrochemicals, Lp | Apparatus for preparing polyolefin products and methodology for using the same |
-
1995
- 1995-04-21 MY MYPI9501048 patent/MY131071A/en unknown
- 1995-04-24 TW TW84104024A patent/TW316267B/zh not_active IP Right Cessation
- 1995-04-28 CN CNB951047469A patent/CN1138795C/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CN1118355A (en) | 1996-03-13 |
| TW316267B (en) | 1997-09-21 |
| MY131071A (en) | 2007-07-31 |
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