Method for removing catalyst in preparation of light color c9 petroleum resin
By using liquid polyol extraction and solid complex filtration, the problems of low catalyst removal efficiency and poor product performance in C9 petroleum resin were solved, achieving light-colored, high-efficiency catalyst removal and resin production.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- GUANGDONG XINHUA YUE RESIN TECH CO LTD
- Filing Date
- 2021-03-26
- Publication Date
- 2026-06-02
AI Technical Summary
Existing technologies for removing catalysts from C9 petroleum resins suffer from environmental pollution, low efficiency, and poor product performance. In particular, alkaline washing methods result in high water consumption and emulsification, while solid-alkali dry washing methods suffer from uneven dispersion and low removal efficiency.
C9 petroleum resin liquid is separated by liquid polyol extraction to form an upper resin liquid and a lower catalyst solution. The resin solution is then reacted with a solid alkali to generate a solid complex. The catalyst is separated by filtration, thus avoiding the problem of uneven dispersion in the solid alkali dry cleaning process.
The catalyst was efficiently removed, and the resulting petroleum resin was light in color, low in ash, and had excellent performance. Furthermore, the polyols could be recycled, which reduced production costs.
Abstract
Description
Technical Field
[0001] This invention relates to the field of petroleum resins, and more specifically to a method for removing catalysts in the preparation of light-colored C9 petroleum resins. Background Technology
[0002] C9 petroleum resin is a thermoplastic solid resin polymerized primarily from C9 (carbon chain length of 9 carbon atoms) fractions produced as a byproduct of ethylene cracking.
[0003] In the production process of C9 petroleum resin, boron trifluoride (BF3) is usually used as a catalyst for polymerization. After polymerization, the catalyst in the polymerization liquid needs to be removed before vacuum distillation can be carried out to obtain the final product.
[0004] Currently, there are two methods for removing catalysts:
[0005] The first method is alkaline washing. The alkaline washing neutralization process not only consumes a large amount of water, causing environmental pollution, but also may involve emulsification, leaving alkaline residue generated during the neutralization reaction in the resin solution, which has an adverse effect on product performance. In addition, the wastewater after neutralization contains a large amount of fluoride ions and cannot be discharged directly. It needs to be treated by professional fluoride-containing water treatment equipment before it can be discharged to the factory's wastewater treatment plant.
[0006] The second method is solid alkali dry cleaning, which commonly uses solid calcium hydroxide for neutralization and filtration to remove the catalyst in the resin polymerization liquid. However, because solid alkalis such as calcium hydroxide cannot be well dispersed in the resin polymerization liquid, the removal efficiency is low. Moreover, the small-particle-size calcium fluoride and calcium tetrafluoroborate generated by neutralization can easily enter the resin polymerization liquid, resulting in poor performance of the resin product. Summary of the Invention
[0007] This invention provides a method for removing catalysts in the preparation of light-colored C9 petroleum resin. The method involves adding a liquid polyol to the C9 petroleum resin solution for extraction. After separation, a solid alkali is added to the resulting polyol extract to neutralize the catalyst, forming a solid complex precipitate. This precipitate is then separated from the polyol by filtration. This method efficiently removes the catalyst, and the produced petroleum resin has a light color, low ash content, and good performance indicators.
[0008] The objective of this invention is achieved through the following technical solution:
[0009] A method for removing catalysts in the preparation of light-colored C9 petroleum resin involves adding a polyol to a C9 petroleum resin solution, extracting, allowing it to stand, and separating the layers to obtain an upper layer of light-colored C9 petroleum resin solution and a lower layer of polyol solution containing the catalyst, thereby removing the catalyst. This invention avoids the problem of uneven solid-liquid distribution during the solid-alkali dry cleaning process by adding liquid polyol to the C9 petroleum resin solution. Furthermore, because the density of the polyol is greater than that of the resin solution, the polyol extract settles to the lower layer of the system, facilitating separation.
[0010] Furthermore, in this invention, a solid alkali is added to the polyol solution containing the catalyst, and the mixture is stirred. The catalyst reacts with the solid alkali to form a solid complex. The polyol and the solid complex are separated by filtration, and the polyol is recovered. In this step, the reaction temperature is 30-40°C.
[0011] The amount of polyol added is 5% to 30% of the mass fraction of the C9 petroleum resin liquid. The polyol is at least one of ethylene glycol, glycerol, and butanediol.
[0012] The amount of solid alkali added is 2-6 times the molar amount of the catalyst, preferably 3-4 times. The solid alkali is one of calcium hydroxide, sodium hydroxide, and potassium hydroxide; calcium hydroxide is preferred.
[0013] The preparation method of C9 petroleum resin liquid according to the present invention is as follows: C9 fraction undergoes a polymerization reaction in the presence of an inert solvent and a catalyst to obtain C9 petroleum resin liquid. The reaction temperature is 10-40℃, and the reaction time is 2-6 h; preferably, the reaction temperature is 20-30℃, and the reaction time is 3-5 h.
[0014] The catalyst is a Lewis acid, including boron trifluoride gas, boron trifluoride diethyl ether complex, and aluminum trichloride, etc. Its addition amount is 0.3-3% of the C9 fraction by mass; preferably, the addition amount is 0.6-1% of the C9 fraction by mass.
[0015] The beneficial effects of this invention are:
[0016] (1) The resin product prepared by the present invention has a light color and almost no ash content.
[0017] (2) The catalyst of the present invention has a significant effect on removing the catalyst from the resin liquid, and the removal time of the catalyst from the resin liquid is short, thereby improving production efficiency.
[0018] (3) The polyols used in this invention can be recycled and reused, which reduces the cost for enterprises. Detailed Implementation
[0019] The following embodiments are preferred embodiments of the present invention and are only used to facilitate the illustration of the present invention. They are not intended to limit the present invention in any way. Any person skilled in the art who makes local modifications or alterations to the technical content disclosed in the present invention without departing from the scope of the technical features of the present invention shall still fall within the scope of the technical features of the present invention.
[0020] The testing methods for each indicator in this invention are as follows:
[0021] Softening point: The ring and ball method specified in GB / T24138-2009 was used for determination. The instrument used was the SYD-2806H fully automatic softening point tester manufactured by Shanghai Changji Geological Instrument Co., Ltd.
[0022] Hue: The Gardner colorimetric method according to GB / T22295-2008 was used for analysis. The instrument used was a PFXI195 colorimeter manufactured by LOVIBOND in the UK.
[0023] Ash content: Analyzed using a high-temperature resistance test chamber (muffle furnace) according to the method of GB / T2295-2008.
[0024] Example 1
[0025] 200g of C9 fraction and 100g of toluene were added to a 1L four-necked flask equipped with a stirrer. Nitrogen gas was introduced for protection, and the flask was kept at a constant temperature of 20°C in a water bath. The stirrer was started at a speed of 60r / min, and 1.2g (0.6%) of boron trifluoride diethyl ether complex catalyst was slowly added dropwise. After reacting at 20°C for 3 hours, 20g of ethylene glycol adsorption catalyst was added to the four-necked flask, and the mixture was stirred at 60r / min for 10 minutes. The mixture was then allowed to stand and the liquid was separated. After 3 minutes, the liquid was separated, and the clear resin polymerization liquid was transferred to a 500ml four-necked flask. The mixture was then subjected to vacuum distillation at -0.08MPa to obtain the C9 petroleum resin product at a distillation temperature of 220°C. In addition, 4.8 g of solid calcium hydroxide was added to the lower layer of ethylene glycol solution. After stirring at 60 r / min for 5 min at 30 °C, the solution was filtered through 80 mesh filter paper at -0.03 MPa. The filter paper contained calcium salt precipitate of boron trifluoride catalyst and excess calcium hydroxide. 19.5 g of ethylene glycol was obtained in the filter flask and recycled.
[0026] The C9 fraction contains: 30% methylstyrene, 0.2% dicyclopentadiene, 10% indene, 45% methyl indene, and 14.8% other components.
[0027] The resin product test results are as follows: yield 63%, softening point 126℃, hue 4.3#, ash content 0%.
[0028] The yield of ethylene glycol was 97.5%.
[0029] Example 2
[0030] 200g of C9 fraction and 100g of toluene were added to a 1L four-necked flask equipped with a stirrer. Nitrogen gas was introduced for protection, and the mixture was kept at a constant temperature of 30°C in a water bath. Stirring was started at 60 rpm, and 2g (1%) of boron trifluoride diethyl ether complex catalyst was slowly added dropwise. After reacting for 3 hours, 30g of glycerol adsorption catalyst was added, and the mixture was stirred at 60 rpm for 15 minutes. The mixture was then allowed to stand and separate. After 3.5 minutes, the separation was complete, and the clear resin polymerization liquid was transferred to a 500ml four-necked flask. The mixture was then subjected to vacuum distillation at -0.09 MPa at 240°C to obtain the C9 petroleum resin product. Separately, 8g of solid calcium hydroxide was added to the lower glycerol solution. The mixture was stirred at 60 rpm for 10 minutes at 30°C, and then filtered through 100-mesh filter paper at -0.02 MPa. The filter paper contained calcium salt precipitate of boron trifluoride catalyst and excess calcium hydroxide. 29.4g of glycerol was obtained in the filter flask and recycled.
[0031] The C9 fraction contains: 25% methylstyrene, 0.3% dicyclopentadiene, 15% indene, 40% methyl indene, and 19.7% other components.
[0032] The resin product test results are as follows: yield 65%, softening point 130℃, hue 4.5#, ash content 0%.
[0033] The yield of glycerol was 98%.
[0034] Example 3
[0035] 200g of C9 fraction and 100g of xylene were added to a 1L four-necked flask equipped with a stirrer. Nitrogen gas was introduced for protection, and the flask was kept at a constant temperature of 28°C in a water bath. The stirrer was started at a speed of 60r / min, and 4g (2%) of boron trifluoride diethyl ether complex catalyst was slowly added dropwise. After reacting for 4 hours, 40g of butanediol was added to terminate the reaction. The mixture was stirred at a speed of 60r / min for 10 minutes and then allowed to stand for separation. After 5 minutes, the separation was completed. The clear resin polymerization liquid in the upper layer was transferred to a 500ml four-necked flask and subjected to vacuum distillation at a pressure of -0.097MPa to obtain the C9 petroleum resin product at a distillation temperature of 200°C. In addition, 15g of solid calcium hydroxide was added to the lower layer of butanediol solution, and stirred at 60r / min for 10min at 30℃. The mixture was then filtered through 60-mesh filter paper at -0.03MPa. The filter paper contained calcium salt precipitate of boron trifluoride catalyst and excess calcium hydroxide. 38.2g of butanediol was obtained in the filter flask and recycled.
[0036] The C9 fraction contains: 20% methylstyrene, 0.5% dicyclopentadiene, 20% indene, 40% methyl indene, and 19.5% other components.
[0037] The resin product test results are as follows: yield 55%, softening point 122℃, hue 4.7#, ash content 0%.
[0038] The yield of butanediol was 95.5%.
[0039] Example 4
[0040] 200g of C9 fraction and 100g of toluene were added to a 1L four-necked flask equipped with a stirrer. Nitrogen gas was introduced for protection, and the flask was kept at a constant temperature of 25°C in a water bath. Stirring was started at 80 rpm, and 6g (3%) of boron trifluoride diethyl ether complex catalyst was slowly added dropwise. After reacting for 5 hours, 20g of glycerol was added to terminate the reaction. The mixture was stirred at 80 rpm for 15 minutes, then allowed to stand for separation. After 2 minutes of separation, the clear upper layer of resin polymerization solution was transferred to a 500ml four-necked flask and subjected to vacuum distillation at -0.09 MPa at 240°C to obtain the C9 petroleum resin product. Separately, 20g of solid sodium hydroxide was added to the lower glycerol solution. The mixture was stirred at 60 rpm for 20 minutes at 30°C, and then filtered through 60-mesh filter paper at -0.02 MPa. The filter paper contained sodium salt precipitate of boron trifluoride catalyst and excess sodium hydroxide. 19.6g of glycerol was obtained in the filter flask and recycled.
[0041] The C9 fraction contains: 25% methylstyrene, 0.3% dicyclopentadiene, 15% indene, 40% methyl indene, and 19.7% other components.
[0042] The resin product test results are as follows: yield 52%, softening point 127℃, hue 4.6#, ash content 0%.
[0043] The yield of glycerol was 98%.
[0044] Example 5
[0045] 200g of C9 fraction and 100g of toluene were added to a 1L four-necked flask equipped with a stirrer. Nitrogen gas was introduced for protection, and the flask was kept at a constant temperature of 20°C in a water bath. The stirrer was started at a speed of 60r / min, and 0.6g (0.3%) of boron trifluoride diethyl ether complex catalyst was slowly added dropwise. After reacting for 5 hours, 10g of ethylene glycol was added to terminate the reaction. The mixture was stirred at a speed of 60r / min for 15 minutes and then allowed to stand for separation. After 3 minutes, the separation was completed. The clear resin polymerization liquid in the upper layer was transferred to a 500ml four-necked flask and distilled under reduced pressure at -0.085MPa to obtain the C9 petroleum resin product at a distillation temperature of 240°C. In addition, 2.4 g of potassium hydroxide solid was added to the lower layer of ethylene glycol solution. After stirring at 60 r / min for 20 min at 40 °C, the solution was filtered through 80 mesh filter paper at -0.02 MPa. The filter paper contained potassium salt precipitate of boron trifluoride catalyst and excess potassium hydroxide solid. 9.5 g of ethylene glycol was obtained in the filter flask for recycling.
[0046] The C9 fraction contains: 30% methylstyrene, 0.3% dicyclopentadiene, 10% indene, 45% methyl indene, and 14.7% other components.
[0047] The resin product test results are as follows: yield 68%, softening point 137℃, hue 4.6#, ash content 0%.
[0048] The yield of ethylene glycol was 95%.
[0049] Comparative Example 1
[0050] 200g of C9 fraction and 100g of toluene were added to a 1L four-necked flask equipped with a stirrer. Nitrogen gas was introduced for protection, and the flask was kept at a constant temperature of 20°C in a water bath. The stirrer was started at a speed of 60r / min, and 1.2g of boron trifluoride diethyl ether complex catalyst was slowly added dropwise. After reacting at 20°C for 3 hours, 100g of aqueous solution containing 2.4g of sodium hydroxide was added to terminate the reaction. The mixture was allowed to stand and separated, and then washed with water until neutral before separating again. The total separation time was 45min. The upper resin polymerization liquid was transferred to a 500ml four-necked flask and subjected to vacuum distillation at -0.09MPa at a distillation temperature of 220°C to obtain the C9 petroleum resin product.
[0051] The C9 fraction contains: 30% methylstyrene, 0.2% dicyclopentadiene, 10% indene, 45% methyl indene, and 14.8% other components.
[0052] The product test results are as follows: yield 61%, softening point 138℃, hue 6.2#, ash content 0.14%.
[0053] Comparative Example 2
[0054] 200g of C9 fraction and 100g of toluene were added to a 1L four-necked flask equipped with a stirrer. Nitrogen gas was introduced for protection, and the flask was kept at a constant temperature of 20°C in a water bath. The stirrer was started at a speed of 60 r / min, and 1.2g of boron trifluoride diethyl ether complex catalyst was slowly added dropwise. After reacting at 20°C for 3 hours, 4.8g of calcium hydroxide solid base was added to terminate the reaction. The mixture was stirred at a speed of 60 r / min for 20 minutes, and then filtered through 80-mesh filter paper at -0.03 MPa. The filtered resin polymerization solution was transferred to a 500ml four-necked flask and subjected to vacuum distillation at -0.09 MPa at a distillation temperature of 230°C to obtain the C9 petroleum resin product.
[0055] The C9 fraction contains: 30% methylstyrene, 0.2% dicyclopentadiene, 10% indene, 45% methyl indene, and 14.8% other components.
[0056] The product test results are as follows: yield 62.3%, softening point 138℃, hue 6.0#, ash content 0.20%.
Claims
1. A process for the removal of catalyst in the preparation of a light colored C9 petroleum resin characterized by, Add polyol to C9 petroleum resin solution, extract, let stand and separate to obtain upper light-colored C9 petroleum resin solution and lower polyol solution containing catalyst, then separate them. A solid base is added to the polyol solution containing the catalyst, and the mixture is stirred. The catalyst reacts with the solid base to form a solid complex. The polyol and the solid complex are separated by filtration, and the polyol is recovered. The catalyst is a boron trifluoride diethyl ether complex catalyst. The amount of polyol added is 10% of the mass fraction of the C9 petroleum resin liquid; The polyol is ethylene glycol; The preparation method of the C9 petroleum resin liquid is as follows: In the presence of an inert solvent and a catalyst, the C9 fraction undergoes a polymerization reaction to obtain the C9 petroleum resin liquid, wherein the reaction temperature is 20℃ and the reaction time is 3h; The amount of solid alkali added is 2-5 times the molar amount of the catalyst; The catalyst is added at a rate of 0.6% of the C9 fraction by mass. The ash content of the obtained resin was 0%.
2. The process for removal of catalyst in the preparation of light color C9 petroleum resin according to claim 1, characterized in that, The solid alkali is any one of calcium hydroxide, sodium hydroxide, and potassium hydroxide.