TWI790010B - Derivative Oligomer Recycling Treatment Method in Manufacturing Process - Google Patents

Abstract

A recycling treatment method for derivatized oligomers in the manufacturing process, mainly dissolving the oligomer wax block with an organic solvent containing a benzene ring (preferably xylene), and then using activated clay as an adsorbent to dissolve the oligomer wax block Carry out adsorption decolorization treatment, the oligomer wax block is treated with the activated clay and the organic solvent containing a benzene ring at an optimal ratio, and the oligomer wax block is dissolved in an organic solvent containing a benzene ring and activated clay After adsorption and decolorization treatment, the content of vinyl acetate (VA) and metal impurities (especially a large amount of iron (Fe)) has been greatly reduced, and it has become a recycled oligomer with no pungent odor and near white color (no longer yellowish brown). Wax blocks can be transformed into recycled products only after proper processing.

Description

Derivative Oligomer Recycling Treatment Method in Manufacturing Process

The present invention relates to a method for recycling and regenerating oligomer derivatives in the manufacturing process, which is mainly to effectively purify the oligomer wax block derived in the manufacturing process, so that the oligomer wax block can be converted into a regenerated oligomer wax block Recycling treatment method.

Press, in the process of polymerizing chemical products, there are often derivative oligomers, the most common example: ethylene/vinyl acetate copolymer (also known as ethylene/vinyl acetate copolymer, English Ethylene Vinyl Acetate, referred to as EVA), which is formed by copolymerization of ethylene (E) and vinyl acetate (VA), except that the oligomers derived from the polymerization process of ethylene/vinyl acetate copolymer (EVA) are wax blocks (WAX), Oligomers of wax blocks (WAX) are also derived from the polymerization process of chemical products such as polyethylene (PE for short), polypropylene (PP for short), etc. Therefore, in this specification, the terms "oligomer", "oligomer wax block", "oligomer (wax block)", "wax block (WAX)" and "wax block" are essentially Both refer to the same item.

If the oligomer wax block derived from the polymerization process is translucent in color, odorless and tasteless, it can be provided to downstream manufacturers for direct simple processing into lubricants, mold release agents, etc. - valuable products for sale and use. However, in recent years, some chemical products (such as EVA) have been adjusted in the process formula, mainly for the production of high-value products. However, after the process formula is adjusted, the derived oligomer wax blocks appear yellow The color and pungent smell make it impossible to directly and simply process it into lubricants, release agents or other valuable products, so downstream manufacturers are less willing to use it. In addition to the unacceptable oligomer wax block derived from the adjustment of the process formula, sometimes the unacceptable oligomer wax block is derived due to the failure of a certain bond in the process. In essence, the wax block contains metal impurities (especially a large amount of iron (Fe) and sometimes due to oxidative deterioration or other unknown substances, etc., resulting in an unsightly yellow-brown appearance. At the same time, the wax block may Due to the variation of the finished product due to residual monomers, etc., there will be a pungent odor, resulting in difficulty in processing and poor reusability. This kind of wax block can be called "impure wax" for easy understanding.

If the oligomer wax block derived from the polymerization process is directly discarded without proper treatment or destroyed and burned as waste, it will cause serious damage to the environment and ecology. Moreover, if the wax block is purified and highly recyclable Utilization value, suitable as lubricant, mold release agent or other valuable products that can be reused downstream. Therefore, if the oligomer derived in the production process is impure wax, how to directly carry out effective purification treatment, among which, the most important thing is to quickly and effectively dissolve the oligomer wax block. After treatment, the main It can regenerate and transform the wax blocks that originally belonged to wastes into useful materials and meet the requirements of recycling wastes. This is an important issue in environmental protection and recycling.

For the oligomer wax block derived from the chemical process, the present invention researches and develops how to carry out effective purification treatment to convert it into a valuable regenerated material product. After long-term efforts and various experiments, the present invention is finally produced.

The reason is that the main purpose of the present invention is to provide an effective purification process for the oligomer wax block derived in the process, especially to quickly and effectively dissolve the oligomer wax block to convert it into a useful material substance Recycling treatment method.

Another main purpose of the present invention is to provide an effective purification process for the oligomer wax blocks derived from the production process, so as to reduce the amount of waste disposal or treatment of the oligomer wax blocks, thereby increasing its economic benefits. Approach.

In order to achieve the above object, the present invention provides a recycling treatment method for oligomer derivatives in the manufacturing process, which uses the oligomer wax block derived in the manufacturing process as the target object for treatment, and undergoes the following processing steps: (1). Dissolving the oligomer wax block; (2). Using activated clay as an adsorbent to perform adsorption and decolorization treatment on the oligomer wax block, and the weight ratio of oligomer wax block: activated clay is above 1:0.1 (3). The mixed solution of oligomer wax block, solvent and activated clay is filtered to remove the activated clay and impurities in the solution; (4). The activated clay is recycled; (5) The solvent in the solution is recovered and collected by thermal evaporation, and it is characterized in that: the solvent is an organic solvent containing a benzene ring, and the weight ratio of the oligomer wax block: organic solvent containing a benzene ring is 1:1~30 between.

In the above-mentioned method for recycling and regenerating the derivatized oligomers in the manufacturing process, the organic solvent containing benzene rings is preferably xylene.

In the above-mentioned recycling treatment method of derivatized oligomers in the manufacturing process, the optimum weight ratio of the oligomer wax block: organic solvent containing benzene ring is 1:10.

In the above-mentioned recycling treatment method of the derived oligomer in the manufacturing process, the optimal weight ratio of the oligomer wax block: activated clay: organic solvent containing benzene ring is 1:0.5:10.

In the above-mentioned processing method of derivatizing oligomers in the process of recycling, after the oligomer wax blocks are dissolved in the organic solvent containing benzene rings and the activated clay is adsorbed and decolorized, they become non-pungent and odor-free and have a color close to white or slightly pale. Transparent recycled oligomer wax block.

Regarding the present invention in order to achieve the above object, the technical means adopted and the effects that can be achieved, the following examples are given to describe in detail, so that they can be fully understood.

The present invention is developed through various research and development experiments, and it is especially suitable for purifying the oligomer wax block derived in the production process, especially for the rapid and effective dissolution treatment of the oligomer wax block, so that the oligomer wax A recycling treatment method in which blocks can be regenerated and transformed into useful materials. As mentioned above, the oligomer wax block contains a large amount of iron and metal impurities, as well as oxidation or other unknown substances, etc., resulting in an unsightly yellow-brown appearance. At the same time, the oligomer wax block has It may be due to factors such as the variation of the finished product caused by the remaining monomers, so there will be pungent odors and other phenomena, so it is necessary to separate the remaining monomers and metal impurities (especially a large amount of iron (Fe)) from the oligomer wax block The needs of releasing, the present invention promptly stipulates a treatment step that can make the oligomer wax block recycle, and then through many experiments to verify the most suitable treatment method, as shown in Figure 1, the present invention determines The processing steps are as follows:

1. Dissolve the oligomer wax block with different solvents.

2. Adsorption decolorization treatment is carried out by mixing different adsorbents for the oligomer wax block.

3. Filter the mixed solution of oligomer wax block, solvent and adsorbent to remove the adsorbent and impurities in the solution.

4. Recycling the adsorbent.

5. The solvent in the solution is recovered and collected by thermal evaporation.

6. The regenerated oligomer wax block after the above treatment can be reused later.

After the above-mentioned processing steps are determined, the present invention is verified. First of all, aiming at the characteristics of residual monomers (such as vinyl acetate) in oligomer wax block, the present invention uses various solvents to dissolve the oligomer wax block, so as to find the specific organic compound with the optimal ratio. Solvent: In the present invention, different solvents containing at least xylene, acetone, isopropanol, cyclohexane, n-hexane, etc. and oligomer wax blocks are mixed into solutions at normal temperature and pressure, and stirred moderately, and then detected and observed one by one The dissolving effects of various solvents on the oligomer wax block, it was found that xylene can have a better dissolving effect. Theoretically, xylene is a mixture of aromatic hydrocarbons ^, which can dissolve some plastic products, and its volatilization rate is relatively slow. It is not volatile during filtration, so it can have a better dissolution treatment effect; then further replace xylene with various "organic solvents containing benzene rings", the experimental results found that organic solvents containing benzene rings can have a good effect on oligomer wax blocks Dissolution treatment effect, but preferably still use xylene as the optimal solvent for dissolving the oligomer wax block.

After selecting the organic solvent containing benzene ring as the solvent that can have an excellent dissolving effect on the oligomer wax block, the present invention further uses the weight ratio of oligomer wax block: xylene to vary from 1:1 to 30 The dissolving treatment of the oligomer wax block was carried out under the ratio, and the dissolution efficiency was evaluated for the wax recovery rate of the regenerated oligomer wax block. The results are shown in Figure 2, and the wax was 70% The recovery rate of more than %, among them, the oligomer wax block: xylene in the weight ratio of 1:10, the wax can have a recovery rate of up to 83%, so consider the filtration time, xylene recovery and reuse and Under various factors of replacement cost, the optimum weight ratio of oligomer wax block: xylene is selected as 1:10. During the above test process of selecting the optimum ratio, the present invention also tried to change the organic solvent containing benzene rings to dissolve the oligomer wax block, and the result was still the oligomer wax block at a weight ratio of 1:10: Optimum ratio of organic solvents containing benzene rings.

During the above-mentioned test process of selecting the optimal ratio, the present invention also tried to use organic solvents containing benzene rings and various solvents to dissolve the oligomer wax block. Paraffin block: the optimal ratio of organic solvents containing benzene rings or various solvents.

Next, the present invention aimed at the characteristic that the oligomer wax block contains a large amount of iron and metal impurities, and carried out adsorption and decolorization experiments on the oligomer wax block with various adsorbent materials to find the most optimal ratio of the adsorbent material. The adsorption decolorization treatment has the effect of both adsorption and decolorization treatment in essence. It mainly absorbs iron and metal impurities in the solution of dissolving oligomer wax blocks, and the filtered wax can greatly reduce the iron content. And the content of metal impurities, even reduced to no, which is equivalent to decolorizing the oligomer wax block. The present invention attempts to place different adsorbent materials comprising at least activated clay and activated carbon into the solution of dissolving oligomer wax blocks, and it is observed that the solution gradually becomes transparent when activated clay is added, which obviously has a better decolorization effect. Therefore, the present invention That is, activated clay is selected as the optimal material for adsorption and decolorization of oligomer wax blocks.

Then further in the oligomer wax block: the organic solvent containing benzene ring (preferably xylene) weight ratio is 1:10, adding activated clay is the adsorption material for the adsorption and decolorization of the oligomer wax block, and The oligomer wax block: activated clay weight ratio of 1:0.1 or more is used for adsorption decolorization treatment, and the results do have the effect of adsorption decolorization. Among them, when the weight ratio is 1:0.5, the oligomer The wax block solution already has obvious decolorization effect, so there is no need to increase the amount of activated clay. Therefore, the present invention selects a weight ratio of 1:0.5 as the optimum ratio of oligomer wax block: activated clay, so the overall In other words, the optimum weight ratio of the oligomer wax block selected in the present invention: organic solvent containing benzene ring: activated clay is 1:10:0.5.

Because there are many other impurities in the oligomer wax block, after the oligomer wax block is dissolved and adsorbed and decolorized, the mixed solution must be filtered once to remove the active clay and other impurities in the mixed solution. and filtered to remove, and then the filtered adsorbent can be regenerated and reused.

Next, the present invention recovers and collects the different solvents in the mixed solution by thermal evaporation, which is to heat the mixed solution so that various solvents (for example: vinyl acetate (VA) and organic solvents containing benzene rings used for dissolution) are separated Evaporate at its boiling point, and then cool down and collect through different pipelines. For example, the organic solvent containing benzene ring is recovered and heated to a temperature above about 130 ^o C. This temperature will exceed the boiling point of vinyl acetate (VA). Therefore, vinyl acetate (VA) VA) will be evaporated and collected first, and then the organic solvent containing benzene ring will be evaporated and collected again. The collected vinyl acetate (VA) can be used as a chemical material, and the organic solvent containing benzene ring recovered by thermal evaporation can be used to dissolve the oligomer wax block or the treated wax again. After the activated clay and impurities in the mixed solution are removed by filtration, and the different solvents are recovered and collected by thermal evaporation, the remaining wax is the purified regenerated oligomer wax block that can be used for subsequent processing.

In order to verify the treatment effect of the present invention, the present invention promptly detects and analyzes the content of vinyl acetate (VA) in the wax of the oligomer wax block before the treatment and the regenerated oligomer wax block after treatment, and the results are shown in Figure 3 As shown, the untreated oligomer wax block contained vinyl acetate (VA) up to 17,700 ppm, and then the oligomer wax block was regenerated after dissolving and adsorption decolorization for detection , wherein, if the experimental grade clay is used for decolorization, the vinyl acetate (VA) contained in the wax can be as low as 12.6 ppm, and if the industrial grade clay is used for decolorization, the vinyl acetate (VA) contained in the wax is 41.1 ppm (also a low value); even if the organic solvent containing benzene ring (preferably xylene) is recycled by thermal evaporation and reused for dissolving treatment, the highest vinyl acetate (VA) contained in the wax of the regenerated oligomer wax block is only Detected 121 ppm, which is quite good. On the whole, the vinyl acetate (VA) in the oligomer wax block has been largely removed after the dissolution treatment of an organic solvent containing a benzene ring (preferably xylene) and the adsorption and decolorization treatment of activated clay, so after the present invention The pungent odor of the oligomer wax block has been greatly eliminated after the advanced treatment method.

As mentioned above, the present invention attempts to recover the xylene solution after dissolving the oligomer wax block by thermal evaporation, and reuse it for dissolving the oligomer wax block, and finds that it still has an excellent dissolution effect, so In Figure 3, when the xylene recovered by the first thermal evaporation is reused to dissolve the oligomer wax block or the treated regenerated oligomer wax block, the sample name is taken as "the first evaporation recovery two Wax after toluene treatment", when the xylene recovered by subsequent evaporation is used to dissolve the oligomer wax block or the treated regenerated oligomer wax block, the sample names are named in sequence. As can be seen from Figure 3, the increase in the number of reuses by thermal evaporation of xylene has no direct correspondence with the content of vinyl acetate (VA). After deliberation, it is known that the factor for the reduction of the content of vinyl acetate (VA) is actually xylene solvent. The temperature of recovery heating is about 130 ^o C, which is obviously much higher than the boiling point of vinyl acetate (VA), so part of vinyl acetate (VA) will escape into the atmosphere. When using organic solvents containing benzene rings to dissolve oligomer wax blocks, the solution of the dissolved organic solvents containing benzene rings is recovered by thermal evaporation and reused for dissolving oligomer wax blocks. There will be a dissolution effect as shown in Figure 3.

Continue, the present invention detects and analyzes the heavy metal content in the wax of the regenerated oligomer wax block after treatment, because the oligomer wax block before treatment contains iron (Fe), and the metals that may be contained in the process equipment are also Iron (Fe) is common, so the present invention detects and analyzes iron (Fe) and common electroplating elements including chromium (Cr), nickel (Ni), and zinc (Zn). The test results are shown in Figure 4. It shows that the iron (Fe) content of the untreated oligomer wax block is 643 mg/kg. The content has been greatly reduced to 13.5 mg/kg (referring to the use of experimental grade clay) or 18.0 mg/kg (referring to the use of industrial grade clay), so it can be seen that the iron element has been greatly adsorbed and transferred to the clay, resulting in the iron content in the clay. significantly increased after treatment, while the rest of the elements decreased before and after treatment.

The original oligomer wax block has been purified into a regenerated oligomer wax block after being dissolved in an organic solvent containing a benzene ring and adsorbed and decolorized with activated clay as an adsorbent. The wax of the polymer wax block is analyzed by heat flow, which is to observe and analyze the wax of the regenerated oligomer wax block with a differential scanning calorimeter (DSC). The temperature was raised from 90 ^o C to 160 ^o C, and after maintaining the temperature for 5 minutes, the temperature was lowered to 90 ^o C. The result is shown in Figure 5. It was endothermic in the heating section, and at -44.32 ^o C and -19.72 ^o There are two glass transition (Tg) temperatures at C, the characteristic temperature is mainly caused by the change of the shape of the non-crystalline polymer, and a very small exothermic peak appears at 34.57 ^o C, which is estimated to be the beginning of crystallization of the polymer to form micro The heat released during the crystallization process shows an exothermic peak at 41.71 ^o C on the cooling curve. The exothermic peak on the cooling curve is estimated to be the Freezing Point, but there is no obvious difference in the test. Wave peaks appear, it can be estimated that the regenerated oligomer wax block of the present invention is an amorphous material.

For the oligomer wax block derived in the manufacturing process, after the dissolution treatment with an organic solvent containing a benzene ring as claimed in the present invention, and the recycling treatment method of using activated clay for adsorption and decolorization treatment, the vinyl acetate (VA) has been greatly reduced. ) and iron (Fe) content, so the oligomer wax block has been effectively purified and turned into a regenerated oligomer wax block without pungent odor and color near white (no longer yellowish brown), so it is no longer a Waste, which is regenerated into useful materials, the regenerated oligomer wax block can be transformed into industrial mold release agent or lubricant or other value after proper processing. product.

From the above description, it can be seen that the present invention is mainly a recycling treatment method for effectively purifying the oligomer wax block derived from the production process, wherein the most important method is to treat the derived oligomer wax block with an organic solvent containing a benzene ring. Dissolving treatment, this step of dissolving the derived oligomer wax block with an organic solvent containing a benzene ring, is never thought of by any conventional treatment method, let alone used, and then in order to produce an excellent treatment effect At the same time, the present invention selects activated clay as the adsorption material to carry out adsorption and decolorization treatment on the derived oligomer wax blocks. It must be emphasized here that the present invention can adopt the oligomer wax blocks, organic solvents containing benzene rings and The three adsorbents of activated clay are put into a dynamic mixing tank or a pipeline for mixing separately or at the same time for simultaneous dissolution treatment and adsorption decolorization treatment. The purification effect produced by them is the same. The operating temperature of the mixing tank is 50 It can be between ~150°C, preferably between 50-70°C; or, the oligomer wax block, the organic solvent containing benzene ring and the adsorption material of activated clay can be put into a static mixture separately or at the same time. Mixing in a container for dissolution treatment and adsorption decolorization treatment, the purification effect produced by it is the same.

In summary, the present invention clearly achieves the expected function and purpose, and the detailed description can enable those skilled in the art to implement it, but the above-mentioned embodiments are only used to illustrate the present invention, and all equivalent structures The change still does not depart from the scope of the patent of the present invention.

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Shown in Fig. 1 is the flow block diagram of the steps of the recycling treatment method of the present invention. Shown in Fig. 2 is the wax recovery schematic diagram of solvent consumption and regenerated oligomer wax block in the present invention Shown in Fig. 3 is vinyl acetate (VA) content detection and analysis schematic diagram in the present invention. Figure 4 shows a schematic diagram of the detection and analysis of heavy metal content in the present invention. Figure 5 is a graph showing the heat flow analysis of the wax of the regenerated oligomer wax block according to the present invention.

Claims (3)

A recycling treatment method for oligomer derivatives in the manufacturing process, which uses the oligomer wax block derived in the manufacturing process as the target object for treatment, and undergoes the following processing steps: (1) dissolving the oligomer wax block with a solvent; 2) Adsorb and decolorize the oligomer wax block with activated clay as an adsorbent, and the weight ratio of oligomer wax block: activated clay is more than 1:0.1; (3) mix oligomer wax block, solvent and the mixed solution of activated clay is filtered to remove the activated clay and impurities in the solution; (4) the solvent in the solution is recovered and collected by thermal evaporation, and it is characterized in that: the solvent is xylene, and the The weight ratio of oligomer wax block: xylene is between 1:1~30. The method for recycling and regenerating oligomers derived in the manufacturing process as described in Claim 1, wherein the optimal weight ratio of the oligomer wax block:xylene is 1:10. The method for recycling oligomer derivatives in the production process as described in claim 1, wherein, after the xylene is dissolved and the activated clay is adsorbed and decolorized, the oligomer wax block becomes non-pungent and odorous and has a color close to white Or slightly transparent regenerated oligomer wax block.

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