Production method for synchronous co-production of terpene resin and titanium dioxide

Abstract

The invention provides a production method for synchronous co-production of terpene resin and titanium dioxide, and belongs to the technical field of coupling preparation of chemical resin and inorganic functional materials. The production method comprises the following steps: mixing an organic solvent and titanium tetrachloride to obtain a mixed solution; under the condition of protective gas, a pinene raw material is dropwise added into the mixed solution for a reaction, and a terpene stock solution is obtained; adding water into the terpene stock solution for washing at the washing temperature of 70-90 DEG C to obtain a white turbid solution, filtering the white turbid solution to obtain white filter residues and filtrate, and heating and drying the white filter residues to obtain titanium dioxide; and separating the terpene resin from the filtrate. The titanium element in the catalyst is recovered, and chloride ions in titanium tetrachloride are utilized to catalyze the polymerization of the terpene resin, so that the problems that the catalyst cannot be recovered and the wastewater is difficult to treat in the traditional terpene resin process are solved, the synchronous co-production of the high-purity titanium dioxide by the light-color terpene resin is realized, and the adaptation of a regional industrial chain is facilitated.

Description

Technical Field

[0001] This invention relates to the field of chemical resin and inorganic functional material coupling preparation technology, specifically to a production method for the simultaneous co-production of titanium dioxide from terpene resin. Background Technology

[0002] Terpene resins, as important green polymer materials, are widely used in adhesives, coatings, inks, and other fields. Their traditional synthesis process uses α-pinene, β-pinene, turpentine, and other raw materials, employing Lewis acids such as aluminum trichloride and boron trifluoride as catalysts. However, this process suffers from the following core technical problems: (1) The catalyst cannot be recovered, resulting in serious waste of resources: After the reaction, aluminum chloride and boron trifluoride need to be washed away by water multiple times. The aluminum ions and boron ions completely enter the wastewater, which not only loses the resource value of the catalyst, but also leads to the concentration of heavy metal ions in the wastewater as high as 500-800 mg / L, increasing the subsequent treatment cost by 30%-40%.

[0003] (2) The product is difficult to separate and the quality is unstable: aluminum hydroxide flocs are generated when aluminum trichloride is washed with water. These flocs are easy to form an emulsion system with terpene resin, which is difficult to wash. It takes 4-6 water washes to make the pH of the organic phase neutral, resulting in a resin yield loss of 5%-8%. In addition, the residual aluminum ions will increase the resin color number to 7-9, affecting the application of the product in high-end fields.

[0004] (3) Product quality needs to be improved: using aluminum trichloride as a catalyst and turpentine and α-pinene as raw materials, the synthesized terpene resin is liquid with a softening point of up to 60℃; or using aluminum trichloride as a catalyst and a mixture of α-pinene and β-pinene as raw materials, the color number is above 6; if aluminum trichloride and silicon tetrachloride are mixed as catalysts, silicate crystals will appear on the glass reactor during the reaction process and cannot be washed off.

[0005] (4) Poor industrial chain synergy: Traditional processes focus only on a single product of terpene resin and do not form a linkage with other industries in the region (such as the titanium dioxide industry). The intermediate titanium tetrachloride (purity ≥95%) produced in the production of titanium dioxide often requires additional processing to obtain high-purity titanium dioxide, resulting in idle cross-industry resources.

[0006] To address the aforementioned issues, existing technologies primarily focus on optimizing wastewater treatment processes (such as flocculation and sedimentation, and membrane separation), but fail to address the root cause of the problem of synergistic improvement in catalyst recovery and product quality. Some studies have attempted to use titanium-based catalysts, but have not established a mechanism for the co-production of titanium dioxide from terpene resins, nor have they achieved coupling and integration with the regional titanium industry, making industrialization difficult.

[0007] For example, Chinese patent document CN109721468A discloses a method for preparing terpineol by isomerization of α-pinene. This method uses a microporous aluminum silicate molecular sieve loaded with titanium chloride as a catalyst. α-pinene undergoes catalytic isomerization under the action of the catalyst. The reaction is stirred for 6-9 hours to obtain camphene mother liquor. The reaction temperature is 110℃-130℃. During the reaction, the evaporated gas is condensed and refluxed through a cooling device at the top of the reactive distillation column. This method only uses titanium chloride as a catalyst and does not address how to achieve the co-production of titanium dioxide from terpene resin, or how to prepare light-colored terpene resin and high-purity titanium dioxide. Summary of the Invention

[0008] In view of this, the present invention provides a method for the simultaneous co-production of titanium dioxide from terpene resin, which recovers titanium from the catalyst and utilizes chloride ions from titanium tetrachloride to catalyze the polymerization of terpene resin. This solves the problems of unrecoverable catalysts and difficult wastewater treatment in traditional terpene resin processes, and simultaneously achieves the simultaneous co-production of high-purity titanium dioxide from light-colored terpene resin, which is convenient for regional industrial chain adaptation.

[0009] To achieve the above objectives, the present invention provides a method for the simultaneous co-production of titanium dioxide from terpene resin, comprising the following steps: (1) Mix organic solvent and titanium tetrachloride to obtain a mixed solution; under protective gas conditions, add pinene raw material dropwise to the mixed solution to carry out the reaction. After the reaction is completed, terpene stock solution is obtained. (2) Add water to the terpene stock solution and wash at a temperature of 70-90℃ to obtain a white turbid liquid. Filter the white turbid liquid to obtain a white filter residue and filtrate. Heat and dry the white filter residue to obtain titanium dioxide. (3) The terpene resin was separated from the filtrate.

[0010] The present invention uses titanium tetrachloride as both a catalyst and a titanium source to achieve the simultaneous co-production of titanium dioxide from terpene resin, realize catalyst recovery, and facilitate the separation of catalyst and terpene resin. In order to obtain high-purity titanium dioxide, light-colored terpene resin is obtained, thereby improving the quality of terpene resin.

[0011] In step (1), the protective gas is nitrogen or argon, etc. The protective gas is used to isolate water in the air and prevent the catalyst from being deactivated by water. In step (2), the washing temperature is 70-90℃. Below 70℃, the washing solution is emulsion-like and cannot effectively separate the organic phase and the aqueous phase; above 90℃, the water is prone to boiling and the amount of organic solvent carried by the water to evaporate increases.

[0012] The pinene raw material of this invention is added dropwise, which facilitates the obtaining of terpene resin with a uniform molecular weight distribution and ensures a high yield of terpene resin. In contrast, when α-pinene is added directly and instantaneously without dropwise addition, a large amount of exothermic reaction occurs within a few minutes, causing a rapid temperature rise in the reactor. This can lead to the following problems: the temperature exceeds the boiling point of the organic solvent, causing the material in the reactor to boil and splash out; even if the temperature does not exceed the boiling point of the organic solvent, the polymerization reaction is still highly exothermic, and after the initial exothermic peak, the temperature drops rapidly, resulting in a largely non-uniform product with low yield and a large molecular weight distribution. Even with prolonged heat preservation, such as 5 hours, polymerization only occurs in the first few minutes after the large amount of α-pinene is added; the subsequent reaction is essentially halted after the initial few minutes of exothermic reaction, resulting in low product yield.

[0013] Furthermore, the pinene raw material is α-pinene, β-pinene, or turpentine oil. The turpentine oil, such as industrial-grade turpentine oil, has a terpene content ≥87 wt.%.

[0014] Turpentine is a liquid extracted from the resin of coniferous plants through distillation or other methods. Its main components are terpenes, such as α-pinene and β-pinene, and it is suitable for the economic systems of areas rich in forestry and titanium mineral resources (such as Guangxi).

[0015] Further, in step (1), titanium tetrachloride is 1%-15% of the weight of pinene raw material, for example, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 11%, 12%, 13%, 14%, 15%, etc.; preferably, titanium tetrachloride is 2%-10% of the weight of pinene raw material.

[0016] Further, the organic solvent is 0.3-2% of the mass of the terpene raw material, for example 0.3, 0.5, 0.6, 0.8, 1.0, 1.2, 1.3, 1.5, 1.6, 1.8, 1.9, 2.0, etc., and preferably, the organic solvent is 0.9-1.2% of the mass of the terpene raw material.

[0017] Further, in step (1), under the conditions of 20-25℃ and stirring, the dropping time of pinene raw material is 1-3 hours, such as 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, etc., preferably, the dropping time of pinene raw material is 1.5-2.5 hours; After the addition is complete, continue the reaction at a constant temperature for 2-3 hours, such as 2 hours, 2.5 hours, 3 hours, etc. Preferably, continue the reaction at a constant temperature for 2.5-3 hours.

[0018] Furthermore, the organic solvent is one or more of toluene, xylene, and cyclohexane.

[0019] Furthermore, in step (1), the titanium tetrachloride is derived from commercially available titanium tetrachloride or an intermediate produced by the chloride process for titanium dioxide, and the TiCl4 content of the intermediate is ≥95wt.%.

[0020] Titanium tetrachloride is an intermediate produced by the chloride process of titanium dioxide. Because the TiCl4 content of this intermediate is ≥95wt.%, its purity is high and can meet the reaction requirements, making it easy to combine with the production of titanium dioxide by the chloride process.

[0021] Furthermore, the titanium dioxide contains ≥98% TiO2. The production method of this invention facilitates the acquisition of high-purity titanium dioxide.

[0022] Further, in step (3), the filtrate is dehydrated and washed until neutral, then distilled and stripped to obtain terpene resin. The terpene resin has a color of 3-6, such as 3, 4, 5, 6, etc.; preferably, the terpene resin has a color of 3-4. The generation method of the present invention facilitates the acquisition of light-colored terpene resin.

[0023] Further, in step (2), water of equal mass to the organic solvent is added to the terpene stock solution for washing; and the solution is dried at 170-200°C for 1.5-3 hours.

[0024] Furthermore, in step (2), the washing temperature is 70-90℃, such as 70℃, 75℃, 80℃, 85℃, 90℃, etc.; preferably, the washing temperature is 80-90℃.

[0025] The above-described technical solution of the present invention has at least the following beneficial effects: This invention solves the problems of catalyst non-recovery and wastewater treatment difficulties in traditional terpene resin processes. It also realizes the resource utilization of titanium, optimizes the appearance quality of terpene resin, and produces terpene resin with a color number of 3-6, thus reducing the color number in Ghana and broadening the application fields of terpene resin.

[0026] The titanium tetrachloride of this invention has the dual functions of "catalytic polymerization" and "titanium source supply"—Cl - As the Lewis acid active center, it forms a coordination intermediate with the double bond of the terpene raw material, promoting the cationic polymerization reaction; Ti 4+ It is converted into TiO2 during the hydrolysis stage, thus avoiding the waste of metal ions in traditional catalysts.

[0027] This invention ensures a synergistic improvement in the selectivity of the polymerization reaction (PDI of terpene resin molecular weight distribution = 1.8-2.2) and the purity of titanium dioxide (TiO2 ≥ 98%) by linking three parameters: temperature, catalyst dosage, and dropping rate.

[0028] The pinene raw material of this invention can be turpentine oil, and the titanium tetrachloride can be titanium tetrachloride intermediate produced by the chloride process of titanium dioxide. This facilitates regional industrial chain adaptation and is especially suitable for the circular economy system in areas rich in forestry and titanium ore resources (such as Guangxi). It realizes the efficient utilization of terpene raw materials and titanium-based catalysts and the reduction of pollutants. For example, by using local turpentine oil in Guangxi (annual output of over 100,000 tons) as terpene raw material and using titanium tetrachloride intermediate from local chloride process titanium dioxide plants (such as a titanium company in Guangxi), the raw material transportation cost can be reduced (by 15%-20%), forming a regional circular chain of "turpentine oil processing → terpene resin → titanium dioxide". Attached Figure Description

[0029] Figure 1 The images show the physical samples of the terpene resins prepared in Examples 1-4 and Comparative Examples 1-3. Detailed Implementation

[0030] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the described embodiments of the present invention are within the scope of protection of the present invention.

[0031] Unless otherwise specified in the examples and comparative examples, titanium tetrachloride was commercially available and purchased from Maclean's titanium tetrachloride.

[0032] Example 1 A method for simultaneously producing titanium dioxide from terpene resin includes the following steps: (1) Add 200g toluene and 12g titanium tetrachloride to a 1L four-necked flask to obtain a mixed solution. Purge nitrogen gas and add 200g α-pinene dropwise under stirring for 2 hours. After the addition is complete, continue to keep the reaction at the temperature for 3 hours. Control the temperature inside the vessel at 20-25℃ during the addition and heat preservation process. After the reaction is completed, the terpene stock solution is obtained. (2) Add 200g of water to the terpene stock solution for washing at 90℃ to obtain a white turbid liquid. Filter the white turbid liquid through a G5 sintered sand core funnel and collect the white filter residue and filtrate. Dry the white filter residue at 180℃ for two hours to obtain 4.6g of titanium dioxide with a recovery rate of 95.83% and a purity of 98%. The purity test method refers to standard GB / T 1706-2006. (3) Remove water from the filtrate and wash until neutral. Distill to 240°C and strip to obtain 181g of yellow solid resin with a color of 3. [The color was measured by the (Fe-Co) colorimetric method, the same below], yield 90.5%, softening point 102°C.

[0033] Example 2 A method for simultaneously producing titanium dioxide from terpene resin includes the following steps: (1) Add 100g cyclohexane, 100g toluene and 20g titanium tetrachloride to a 1L four-necked flask to obtain a mixed solution. Purge nitrogen gas, stir, and add 200g α-pinene dropwise over 2 hours. After the addition is complete, continue to keep the reaction at a constant temperature for 2 hours. During the addition and heat preservation process, control the temperature inside the vessel at 20-25℃. After the reaction is complete, obtain the terpene stock solution. (2) Add 200g of water to the terpene stock solution for washing at 90℃ to obtain a white turbid liquid. Filter the white turbid liquid through a G5 sintered sand core funnel to obtain a white filter residue and filtrate. Dry the white filter residue at 180℃ for two hours to obtain 7.5g of titanium dioxide with a recovery rate of 93.75%. (3) Remove water from the filtrate and wash until neutral. Distill to 240°C and strip to obtain 186g of brownish-yellow solid resin with a color of 4, a yield of 93%, and a softening point of 100°C.

[0034] Example 3 A method for simultaneously producing titanium dioxide from terpene resin includes the following steps: (1) Add 200g of cyclohexane and 4g of titanium tetrachloride to a 1L four-necked flask, purge with nitrogen, stir, and add 200g of α-pinene dropwise over 2 hours. After the addition is complete, continue to keep the reaction warm for 2 hours. During the addition and warming process, control the temperature inside the vessel at 20-25℃. After the reaction is complete, the terpene stock solution is obtained. (2) Add 200g of water to the terpene stock solution for washing at 90℃ to obtain a white turbid liquid. Filter the white turbid liquid through a G5 sintered sand core funnel to obtain a white filter residue and filtrate. Dry the white filter residue at 180℃ for two hours to obtain 1.4g of titanium dioxide with a recovery rate of 87.5%. (3) Remove water from the filtrate and wash until neutral. Distill to 240°C and strip to obtain 166g of brownish-yellow solid resin with a color of 3, a yield of 83%, and a softening point of 85°C.

[0035] Example 4 A method for simultaneously producing titanium dioxide from terpene resin includes the following steps: (1) Add 200g xylene and 8g titanium tetrachloride to a 1L four-necked flask, purge with nitrogen, stir, and add 200g α-pinene dropwise over 2 hours. After the addition is complete, continue to keep the reaction at the temperature for 3 hours. During the addition and temperature keeping process, control the temperature inside the vessel at 20-25℃. After the reaction is complete, the terpene stock solution is obtained. (2) Add 200g of water to the terpene stock solution for washing at 90℃ to obtain a white turbid liquid. Filter the white turbid liquid through a G5 sintered sand core funnel to obtain white filter residue and filtrate. Dry the white filter residue at 180℃ for two hours to obtain 2.9g of titanium dioxide with a recovery rate of 90.6%. (3) Remove water from the filtrate and wash until neutral. Distill to 240°C and strip to obtain 180 g of brownish-yellow solid resin with a color of 3, a yield of 90%, and a softening point of 95°C.

[0036] Comparative Example 1 A method for producing terpene resin includes the following steps: (1) Add 200g toluene and 12g aluminum trichloride to a 1L four-necked flask, purge with nitrogen, stir, and drop 200g α-pinene over 2 hours. After the addition is complete, continue to keep the reaction warm for 3 hours. During the addition and warming process, control the temperature inside the vessel at 20-25℃. (2) After the reaction was complete, 200g of water was added for washing until neutral. The mixture was then distilled to 240℃ and stripped to obtain 181g of dark yellow liquid resin with a color of 8 and a yield of 90.5%.

[0037] Comparative Example 2 A method for producing terpene resin includes the following steps: (1) Add 200g of cyclohexane and 4g of boron trifluoride ether to a 1L four-necked flask, purge with nitrogen, stir, and drop 200g of α-pinene over 2 hours. After the addition is complete, continue to keep the reaction warm for 2 hours. During the addition and warming process, control the temperature inside the vessel at 20-25℃. (2) After the reaction was complete, 200g of water was added for washing until neutral. The mixture was then distilled to 240℃ and stripped to obtain 186g of yellow liquid resin with a color of 5 and a yield of 93%.

[0038] Comparative Example 3 A method for producing terpene resin includes the following steps: (1) Add 100g cyclohexane, 100g toluene and 20g aluminum trichloride to a 1L four-necked flask, purge with nitrogen, stir, add 200g β-pinene dropwise over 2 hours, and continue to keep the reaction warm for 2 hours after the addition is complete. Control the temperature inside the vessel at 20-25℃ during the addition and heat preservation process. (2) After the reaction is complete, add 200g of water to wash until neutral, distill to 240℃, and strip to obtain 190g of brownish-yellow solid resin with a color of 9, a yield of 95%, and a softening point of 96℃.

[0039] like Figure 1As shown, from left to right, are physical images of the terpene resins from Examples 1, 2, 3, 4, Comparative Examples 1, 2, and 3. Figure 1 It can be seen that the color of the terpene resins in Examples 1-4 is significantly lighter than that in Comparative Examples 1-3.

[0040] Comparative Example 4 A method for simultaneously producing titanium dioxide from terpene resin includes the following steps: (1) Add 200g toluene and 12g titanium tetrachloride to a 1L four-necked flask to obtain a mixed solution. Purge nitrogen gas and add 200g α-pinene dropwise under stirring for 2 hours. After the addition is complete, continue to keep the reaction at the temperature for 3 hours. Control the temperature inside the vessel at 20-25℃ during the addition and heat preservation process. After the reaction is completed, the terpene stock solution is obtained. (2) Add 200g of water to the terpene stock solution for washing. Washing at room temperature resulted in an emulsion that could not separate the organic phase from the aqueous phase, making subsequent experiments impossible.

[0041] Comparative Example 5 A method for simultaneously producing titanium dioxide from terpene resin includes the following steps: (1) Add 200g toluene and 12g titanium tetrachloride to a 1L four-necked flask to obtain a mixed solution. Purge nitrogen gas and add 200g α-pinene dropwise under stirring for 2 hours. After the addition is complete, continue to keep the reaction at the temperature for 3 hours. Control the temperature inside the vessel at 20-25℃ during the addition and heat preservation process. After the reaction is completed, the terpene stock solution is obtained. (2) If no water is added to the terpene stock solution, titanium tetrachloride will not undergo hydrolysis and the terpene stock solution will not change.

[0042] Comparative Example 6 A method for simultaneously producing titanium dioxide from terpene resin includes the following steps: (1) Add 200g toluene and 12g titanium tetrachloride to a 1L four-necked flask to obtain a mixed solution. Purge nitrogen gas and add 200g α-pinene dropwise under stirring for 2 hours. After the addition is complete, continue to keep the reaction at the temperature for 3 hours. Control the temperature inside the vessel at 20-25℃ during the addition and heat preservation process. After the reaction is completed, the terpene stock solution is obtained. (2) Add 200g of water to the terpene stock solution for washing at 60℃. An emulsion is formed, and the organic phase and aqueous phase cannot be separated, so subsequent experiments cannot be carried out.

[0043] Example 5 A method for simultaneously producing titanium dioxide from terpene resin includes the following steps: (1) Add 60g toluene and 2g titanium tetrachloride to a 1L four-necked flask to obtain a mixed solution. Purge nitrogen gas and add 200g industrial grade turpentine oil dropwise under stirring. The dropwise addition time is 1 hour. After the dropwise addition is completed, continue to keep the reaction at the temperature for 3 hours. During the dropwise addition and heat preservation process, control the temperature inside the vessel at 20-25℃. After the reaction is completed, the terpene stock solution is obtained. (2) Add 60g of water to the terpene stock solution for washing at 80℃ to obtain a white turbid liquid. Filter the white turbid liquid through a G5 sintered sand core funnel and collect the white filter residue and filtrate. Dry the white filter residue at 180℃ for two hours to obtain titanium dioxide. (3) Remove water from the filtrate and wash until neutral. Distill to 240°C and strip to obtain terpene resin.

[0044] Example 6 A method for simultaneously producing titanium dioxide from terpene resin includes the following steps: (1) Add 400g toluene and 30g titanium tetrachloride to a 1L four-necked flask to obtain a mixed solution. Purge nitrogen gas and add 200g α-pinene dropwise over 3 hours while stirring. After the addition is complete, continue to keep the reaction at the temperature for 3 hours. Control the temperature inside the vessel at 20-25℃ during the addition and temperature keeping process. After the reaction is complete, obtain the terpene stock solution. (2) Add 400g of water to the terpene stock solution for washing at 70℃ to obtain a white turbid liquid. Filter the white turbid liquid through a G5 sintered sand core funnel and collect the white filter residue and filtrate. Dry the white filter residue at 180℃ for two hours to obtain titanium dioxide. (3) Remove water from the filtrate and wash until neutral. Distill to 240°C and strip to obtain terpene resin.

[0045] Example 7 A method for simultaneously producing titanium dioxide from terpene resin includes the following steps: (1) Add 180g toluene and 12g titanium tetrachloride to a 1L four-necked flask to obtain a mixed solution. Purge nitrogen gas and add 200g α-pinene dropwise over 1.5 hours while stirring. After the addition is complete, continue to keep the reaction at the temperature for 3 hours. Control the temperature inside the vessel at 20-25℃ during the addition and temperature keeping process. After the reaction is complete, the terpene stock solution is obtained. (2) Add 180g of water to the terpene stock solution for washing at 90℃ to obtain a white turbid liquid. Filter the white turbid liquid through a G5 sintered sand core funnel and collect the white filter residue and filtrate. Dry the white filter residue at 180℃ for two hours to obtain titanium dioxide. (3) Remove water from the filtrate and wash until neutral. Distill to 240°C and strip to obtain terpene resin.

[0046] Example 8 A method for simultaneously producing titanium dioxide from terpene resin includes the following steps: (1) Add 200g toluene and 10g titanium tetrachloride to a 1L four-necked flask to obtain a mixed solution. Purge nitrogen gas and add 200g α-pinene dropwise over 2.5 hours while stirring. After the addition is complete, continue to keep the reaction at a constant temperature for 2.5 hours. Control the temperature inside the vessel at 20-25℃ during the addition and temperature keeping process. After the reaction is complete, the terpene stock solution is obtained. (2) Add 200g of water to the terpene stock solution for washing at 90℃ to obtain a white turbid liquid. Filter the white turbid liquid through a G5 sintered sand core funnel and collect the white filter residue and filtrate. Dry the white filter residue at 180℃ for two hours to obtain titanium dioxide. (3) Remove water from the filtrate and wash until neutral. Distill to 240°C and strip to obtain terpene resin.

[0047] Example 9 A method for simultaneously producing titanium dioxide from terpene resin includes the following steps: (1) Add 200g toluene and 16g titanium tetrachloride to a 1L four-necked flask to obtain a mixed solution. Purge nitrogen gas and add 200g β-pinene dropwise under stirring for 2 hours. After the addition is complete, continue to keep the reaction at the temperature for 3 hours. Control the temperature inside the vessel at 20-25℃ during the addition and heat preservation process. After the reaction is completed, the terpene stock solution is obtained. (2) Add 200g of water to the terpene stock solution for washing at 90℃ to obtain a white turbid liquid. Filter the white turbid liquid through a G5 sintered sand core funnel and collect the white filter residue and filtrate. Dry the white filter residue at 180℃ for two hours to obtain titanium dioxide. (3) Remove water from the filtrate and wash until neutral. Distill to 240°C and strip to obtain terpene resin.

[0048] Example 10 A method for simultaneously producing titanium dioxide from terpene resin includes the following steps: (1) 200g of toluene and 12g of intermediate produced by the chloride process of titanium dioxide (the TiCl4 content of the intermediate is ≥95wt.%, and it comes from a titanium company in Guangxi) were added to a 1L four-necked flask to obtain a mixed solution. Nitrogen gas was bubbled in and 200g of α-pinene was added dropwise under stirring. The dropwise addition time was 2 hours. After the dropwise addition was completed, the reaction was kept at a constant temperature for 3 hours. During the dropwise addition and the heat preservation process, the temperature inside the reactor was controlled at 20-25℃. After the reaction was completed, the terpene stock solution was obtained. (2) Add 200g of water to the terpene stock solution for washing at 90℃ to obtain a white turbid liquid. Filter the white turbid liquid through a G5 sintered sand core funnel and collect the white filter residue and filtrate. Dry the white filter residue at 180℃ for two hours to obtain titanium dioxide. (3) Remove water from the filtrate and wash until neutral. Distill to 240°C and strip to obtain terpene resin.

[0049] Compared with Example 1, the titanium tetrachloride in this example is derived from an intermediate in the production of titanium dioxide via the chloride process. The recovery rate and purity of the titanium dioxide, as well as the color and yield of the terpene resin, are basically the same as in Example 1.

[0050] Example 11 A method for simultaneously producing titanium dioxide from terpene resin includes the following steps: (1) Add 240g toluene and 12g titanium tetrachloride to a 1L four-necked flask to obtain a mixed solution. Purge nitrogen gas and add 200g α-pinene dropwise under stirring for 2 hours. After the addition is complete, continue to keep the reaction at the temperature for 3 hours. Control the temperature inside the vessel at 20-25℃ during the addition and heat preservation process. After the reaction is completed, the terpene stock solution is obtained. (2) Add 240g of water to the terpene stock solution for washing at 90℃ to obtain a white turbid liquid. Filter the white turbid liquid through a G5 sintered sand core funnel and collect the white filter residue and filtrate. Dry the white filter residue at 180℃ for two hours to obtain titanium dioxide. (3) Remove water from the filtrate and wash until neutral. Distill to 240°C and strip to obtain terpene resin.

[0051] The above description is merely a preferred embodiment of the present invention and is not intended to limit the implementation of the invention. Those skilled in the art can make other variations or modifications based on the above description. It is neither necessary nor possible to exhaustively describe all possible implementations. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for the simultaneous co-production of titanium dioxide from terpene resin, characterized in that, Includes the following steps: (1) Mix organic solvent and titanium tetrachloride to obtain a mixed solution; under protective gas conditions, add pinene raw material dropwise to the mixed solution to carry out the reaction. After the reaction is completed, terpene stock solution is obtained. (2) Add water to the terpene stock solution and wash at a temperature of 70-90℃ to obtain a white turbid liquid. Filter the white turbid liquid to obtain a white filter residue and filtrate. Heat and dry the white filter residue to obtain titanium dioxide. (3) The terpene resin was separated from the filtrate.

2. The method for producing titanium dioxide simultaneously from terpene resin according to claim 1, characterized in that, The raw materials for pinene are α-pinene, β-pinene, or turpentine.

3. A method for producing titanium dioxide simultaneously from terpene resin according to claim 1 or 2, characterized in that, In step (1), titanium tetrachloride is 1%-15% of the mass of pinene raw material.

4. A method for producing titanium dioxide simultaneously from terpene resin according to claim 1 or 2, characterized in that, The organic solvent is 0.3-2% of the mass of the terpene raw material.

5. A method for producing titanium dioxide simultaneously from terpene resin according to claim 1 or 2, characterized in that, In step (1), pinene is added at 20-25°C with stirring for 1-3 hours. After the addition is complete, the reaction is continued for 2-3 hours.

6. A method for producing titanium dioxide simultaneously from terpene resin according to claim 1 or 2, characterized in that, The organic solvent is one or more of toluene, xylene, and cyclohexane.

7. The method for producing titanium dioxide simultaneously from terpene resin according to claim 1, characterized in that, In step (1), titanium tetrachloride is derived from commercially available titanium tetrachloride or intermediates produced by the chloride process for titanium dioxide, and the TiCl4 content of the intermediate is ≥95wt.%.

8. The method for producing titanium dioxide simultaneously from terpene resin according to claim 1, characterized in that, The TiO2 content in titanium dioxide is ≥98%.

9. The method for producing titanium dioxide simultaneously from terpene resin according to claim 1, characterized in that, In step (3), the filtrate is dehydrated and washed until neutral, then distilled and stripped to obtain terpene resin with a color of 3-6.

10. A method for producing titanium dioxide simultaneously from terpene resin according to any one of claims 1-3, characterized in that, In step (2), water of equal mass to organic solvent is added to the terpene stock solution for washing; and the solution is dried at 170-200℃ for 1.5-3 hours.

Images