A catalyst for solid waste from an oil refinery, its preparation method and application

Abstract

This invention discloses a catalyst for oil refinery solid waste, characterized by using oil refinery solid waste SFCC as raw material, which is roasted, impregnated, and roasted again to obtain an HS-SFCC catalyst with suitable number, intensity, and distribution of Lewis acid sites. This invention utilizes oil refinery solid waste to catalyze the synthesis of high-value-added borneol from turpentine, achieving both the harmlessness and resource utilization of oil refinery solid waste, and the conversion of turpentine into high-value-added products, providing a more economically efficient production technology for the synthesis of borneol from turpentine.

Description

Technical Field

[0001] This invention relates to the regeneration and modification of solid waste from heavy oil catalytic cracking in the petrochemical industry and its application in the fine processing of turpentine to produce high-value-added products. Specifically, it relates to a catalyst for solid waste from oil refineries, its preparation method, and its application. Background Technology

[0002] Turpentine oil is a colorless to pale yellow transparent natural organic compound with a characteristic pine resin aroma. It is mainly extracted through methods such as pine resin steam distillation and pine nut solvent extraction. It can be classified into resin turpentine oil, wood turpentine oil, sulfate turpentine oil, and dry distilled turpentine oil. In my country, turpentine oil generally refers to resin turpentine oil. my country has abundant turpentine oil resources, therefore, it mainly produces resin turpentine oil, with an annual output of 90,000 to 110,000 tons, primarily concentrated in Yunnan, Guangxi, and Guangdong provinces. Turpentine oil is composed of a mixture of terpenes, mainly including monoterpenes such as α-pinene, β-pinene, limonene, camphene, and terpinene. The national standard GB / T12901-2006 "Resin Turpentine Oil" stipulates that turpentine oil with a pinene content greater than 85% is of superior grade. Turpentine oil is the world's most produced essential oil, with a wide range of uses and extremely high cost-effectiveness, applied in many fields such as medicine, fragrance, and agriculture, and is figuratively called "the oil of the tree." Turpentine oil, as a low-cost and abundant biomass resource, can be converted into high-value-added chemicals, a process that is feasible and has enormous commercial potential. α-Pinene is the most important component of turpentine oil and is a raw material for the synthesis of camphor, fragrances, turpentine alcohol, terpene resins, and other fine chemicals such as borneol.

[0003] Turpentine oil can be synthesized into borneol, a high-value-added product, through esterification and saponification. Borneol has anti-inflammatory, analgesic, antipyretic, antibacterial, neuroprotective, and penetration-promoting effects, and is widely used in pharmaceuticals, food, and daily necessities. The 2020 edition of the Chinese Pharmacopoeia specifies that borneol (C...) is the main component of borneol (also known as synthetic borneol). 10 H 18 The content of O) shall not be less than 55%, and camphor (C) 10 H 16 The borneol content must not exceed 0.50%. Synthetic borneol can be divided into orthoborneol (with an inward configuration) and isoborneol (with an outward configuration) based on its spatial structure. Isoborneol is more irritating to the gastric mucosa and has stronger hepatotoxicity, exhibiting certain side effects. Therefore, in the synthesis of borneol, a higher quality borneol with a higher orthoborneol content is preferred.

[0004] Methods for synthesizing borneol include camphor reduction, organomagnesia compound decomposition, biosynthesis, direct hydration of α-pinene, and α-pinene esterification-saponification. Currently, the industrial production of borneol mainly employs a two-step esterification-saponification method. This involves using α-pinene and anhydrous oxalic acid as raw materials, undergoing esterification with catalysts such as boron anhydride, metaboric acid, and metatitanic acid to produce borneol oxalate; borneol oxalate then undergoes hydrolysis and saponification with alkali to produce borneol. The key to this synthetic route is the selection of catalysts in the α-pinene esterification reaction. Using catalysts such as boron anhydride, metaboric acid, and metatitanic acid leads to vigorous reactions, difficulty in control, difficulty in catalyst recovery, high requirements for reaction equipment, and low raw material utilization. Therefore, the development of environmentally friendly and efficient catalysts is imperative. Sulfuric acid and hydrochloric acid can be used as liquid catalysts for the α-pinene esterification reaction, exhibiting high catalytic activity. However, the catalyst is difficult to separate after the reaction, and the liquid acid can corrode the reaction equipment, thus hindering its industrial application. Solid acid catalysts mainly include boron-containing, titanium-containing, sulfonic acid-containing, boron-titanium composite, noble metal-based, and solid superacid catalysts. These catalysts can rapidly separate from the product, but they still suffer from drawbacks such as complex and time-consuming preparation processes, short lifespans, difficulty in reaction control, and excessively high isoborneol content in the borneol product, resulting in low production efficiency for borneol. Currently, ionic liquids, as an environmentally friendly catalyst, have been introduced into the borneol synthesis system, exhibiting good catalytic activity. However, ionic liquids require chloroacetic acid to form a composite catalytic system, and chloroacetic acid poses certain hazards, thus hindering the industrial application of such catalysts.

[0005] Catalytic cracking (FCC) is an important crude oil processing method in the petroleum refining industry. With the long-term operation of FCC equipment, the content of heavy metals Ni and V, as well as coke and alkali metals, continuously increases, leading to a decrease in the activity, selectivity, and hydrothermal stability of FCC catalysts. Deactivated catalysts (SFCC), as solid waste from refineries, still contain highly polluting elements such as Ni and V, and have been included in the "National Hazardous Waste List" since August 1, 2016. Previously, the traditional landfill disposal method for SFCC not only caused soil and water pollution but also resulted in the waste of a large amount of valuable resources. SFCC contains not only national strategic resources such as Ni, V, La, and Ce, but also abundant silicon and aluminum elements. Its main components, zeolite molecular sieves and Al2O3 matrix, possess a large number of micropores and a high specific surface area. Therefore, the harmless and resource-oriented treatment of SFCC is urgently needed. Summary of the Invention

[0006] To address the aforementioned technical issues, a catalyst derived from solid waste from oil refineries is developed. This catalyst is used to prepare high-quality borneol, with turpentine oil and anhydrous oxalic acid as raw materials. This results in a low-cost, short-reaction-time, simpler, and safer method for preparing high-quality borneol.

[0007] To achieve the above objectives, the technical solution provided by the present invention is as follows:

[0008] A catalyst made from solid waste from an oil refinery, using SFCC (solidated carbon dioxide) from an oil refinery as raw material, is obtained through roasting, impregnation, and further roasting. HS-SFCC, a refinery solid waste catalyst with suitable number, intensity and distribution of Lewis acid sites.

[0009] A method for preparing a catalyst from solid waste from an oil refinery includes the following steps:

[0010] (i) The solid waste SFCC from the refinery is roasted in a muffle furnace at 450-650°C for 4-6 hours to remove the coke deposited in the SFCC.

[0011] (ii) Impregnate the SFCC obtained after calcination in step (i) with a sulfuric acid solution of concentration of 1-2 mol / L in a water bath at 25-75°C, according to a liquid-to-solid mass ratio of 1-5, for 6-12 hours. After impregnation, centrifuge and filter to remove the extraction solution and take the filter residue.

[0012] (iii) Wash the filter residue obtained after filtration in step (ii) with deionized water until the pH is 6-7. The obtained material after washing is calcined in a muffle furnace at 350-750℃ for 2-7 hours to obtain sulfuric acid modified refinery solid waste HS-SFCC, which is the refinery solid waste catalyst.

[0013] Preferably, in step (i), the refinery solid waste SFCC is roasted in a muffle furnace at 650°C for 4 hours; in step (iii), the material obtained after washing is roasted in a muffle furnace at 550°C for 4 hours.

[0014] Preferably, in step (ii), the solid-liquid ratio of the SFCC obtained after calcination in step (i) to the sulfuric acid solution is 1:4.

[0015] The application of the refinery solid waste catalyst prepared above in the preparation of high-quality borneol;

[0016] The application includes the following steps:

[0017] (1) Add the refinery solid waste catalyst to turpentine and anhydrous oxalic acid. The amount of catalyst added is 3% to 7% of the total mass of turpentine and anhydrous oxalic acid. Then carry out the esterification reaction at 55 to 105°C for 2 to 7 hours. During the reaction, the stirring speed is 200 r / min to 600 r / min.

[0018] (2) After the reaction is completed, the esterification product and the catalyst are separated by vacuum filtration. The esterification product is dissolved in 20-50g of anhydrous ethanol, and then sodium hydroxide solution is added to carry out the saponification reaction. During the reaction, the stirring speed is 500r / min-600r / min. After the reaction is completed, the ethanol is removed by rotary evaporation. After cooling and crystallization at room temperature, borneol is obtained.

[0019] Preferably, the turpentine oil mentioned in step (1) is turpentine oil with an α-pinene content ≥85%; the molar ratio of turpentine oil to anhydrous oxalic acid is 1:0.2~0.7, that is, n(α-pinene):n(anhydrous oxalic acid)=1:(0.2~0.7), and more preferably the molar ratio of turpentine oil to anhydrous oxalic acid is 1:0.5.

[0020] Preferably, the mass concentration of sodium hydroxide solution in step (2) is 3% to 5%; the mass ratio of esterification product to sodium hydroxide solution in step (2) is 1:1 to 2.

[0021] Preferably, the saponification reaction in step (2) is carried out at 80°C for 1 hour.

[0022] Compared with the prior art, the beneficial effects of the present invention are as follows:

[0023] (1) The catalyst of this invention was obtained by impregnation with sulfuric acid of a specific concentration. By optimizing the number, intensity, and distribution of Lewis acid sites in HS-SFCC, as well as the calcination time, a catalyst with high reactivity and selectivity for the synthesis of borneol from turpentine was obtained.

[0024] (2) This invention uses turpentine oil and anhydrous oxalic acid as raw materials and modified refinery solid waste HS-SFCC as catalyst. It utilizes the high specific surface area, hierarchical pore structure and Lewis acid in the zeolite molecular sieve structure provided by HS-SFCC to effectively improve the esterification reaction activity of α-pinene in turpentine oil and the selectivity for n-borneol ester, thereby realizing the synthesis of high-quality borneol and the directional conversion of turpentine oil into high-quality borneol.

[0025] (3) This invention utilizes solid waste from oil refineries to catalyze the synthesis of high-value-added borneol from turpentine. This not only achieves the harmlessness and resource utilization of solid waste from oil refineries, but also enables the conversion of turpentine into high-value-added products, providing a more economically efficient production technology for the synthesis of borneol from turpentine. Attached Figure Description

[0026] Figure 1 This is a gas chromatogram of turpentine oil, the raw material used in this invention.

[0027] Figure 2 This is a gas chromatogram of the esterified product synthesized in Example 3 of the present invention.

[0028] Figure 3 This is a gas chromatogram of the synthetic borneol prepared in Example 3 of the present invention.

[0029] Figure 4 The gas chromatogram of the esterified product synthesized in Comparative Example 2 is shown.

[0030] Figure 5 The gas chromatogram of the synthetic borneol prepared in Comparative Example 2 is shown. Detailed Implementation

[0031] The specific embodiments are described in detail below with reference to the accompanying drawings, but it should be understood that the scope of protection of the present invention is not limited to the specific embodiments. Unless otherwise specified, the raw materials and reagents used in the embodiments are commercially available. The three-necked flask used in the embodiments is equipped with a stirrer, thermometer, and reflux condenser. The anhydrous oxalic acid used in the embodiments was purchased from Shanghai Maclean Biochemical Technology Co., Ltd. The solid waste from the refinery, namely spent fluidized bed catalytic cracking catalyst (SFCC), was provided by CNPC Guangxi Tiandong Petrochemical General Plant Co., Ltd. Turpentine oil was provided by Guangxi Richeng Forest Products Chemical Co., Ltd. Gas chromatography was used to detect the turpentine oil, and the resulting gas chromatogram is shown below. Figure 1 As shown, the main components are listed in Table 1.

[0032] Table 1. Main components of the gas chromatogram of turpentine oil used in this invention.

[0033] Serial Number compound Molecular formula molecular weight content / % 1 α-Pinene <![CDATA[C 10 H 16 ]]> 136 84.98 2 Camphene <![CDATA[C 10 H 16 ]]> 136 2.16 3 Terpinene <![CDATA[C 10 H 16 ]]> 136 5.11 4 For cymenes, p-Cymene <![CDATA[C 10 H 14 ]]> 134 4.59 5 d-Limonene <![CDATA[C 10 H 16 ]]> 136 3.17

[0034] GC conditions (gas chromatography conditions): An Agilent 7820A gas chromatograph was used. The column was an HP-5MS (30m×0.25mm×0.25μm) capillary column. The detector was a flame ionization detector. The carrier gas was high-purity nitrogen. The fuel gas was high-purity hydrogen. The combustion gas was air. The detector temperature was 280℃. The column inlet pressure was 70 kPa. The split ratio was 50:1. The injection volume was 0.4 μL. The flow rate was 60 mL / min.

[0035] Example 1

[0036] A method for preparing a catalyst from solid waste from an oil refinery, comprising the following steps:

[0037] (i) Weigh 10g of SFCC and place it in a crucible. Place it in a muffle furnace and roast at 650°C for 4 hours to remove the coke deposited in the SFCC. After roasting, grind it through a 160-mesh sieve.

[0038] (ii) Take 10g of SFCC obtained after sieving in step (i), mix it with 40g of sulfuric acid solution with a concentration of 1mol / L, and impregnate it in a water bath at 50℃ with a stirring speed of 150r / min for 12h. After impregnation, centrifuge and filter to remove the extraction solution and take the filter residue.

[0039] (iii) The filter residue obtained after filtration in step (ii) is washed with deionized water until the pH is 6-7. The material obtained after washing is calcined in a muffle furnace at 550°C for 4 hours to obtain sulfuric acid modified refinery solid waste HS-SFCC, which is the refinery solid waste catalyst. After being crushed and passed through a 160-mesh sieve, it is ready for use.

[0040] Example 2

[0041] A method for preparing a catalyst from solid waste from an oil refinery, comprising the following steps:

[0042] (ii) Take 10g of SFCC obtained after sieving in step (i), mix it with 40g of sulfuric acid solution with a concentration of 2mol / L, and impregnate it in a water bath at 50℃ with a stirring speed of 150r / min for 12h. After impregnation, centrifuge and filter to remove the extraction solution and take the filter residue.

[0043] The remaining operations are the same as in Example 1, and a refinery solid waste catalyst is obtained.

[0044] Example 3

[0045] The refinery solid waste catalyst prepared in Example 1 was used to prepare high-quality borneol. The operation steps are as follows:

[0046] (1) Weigh 35g of turpentine oil (α-pinene content ≥85%) and 9g of anhydrous oxalic acid into a three-necked flask equipped with a stirrer, thermometer and reflux condenser, add 1.5g of the refinery solid waste catalyst HS-SFCC prepared in Example 1, and then carry out the esterification reaction at 85°C for 4h, with the stirring speed at 400r / min during the reaction.

[0047] (2) After the reaction was completed, the esterification product and the catalyst were separated by vacuum filtration to obtain 34g of esterification product. The esterification product was dissolved in 50g of anhydrous ethanol and then 50g of 5% NaOH solution was added. The saponification reaction was carried out at 80℃ for 1h with a stirring speed of 500r / min. After the saponification reaction was completed, the ethanol was removed by rotary evaporation and the borneol was obtained after cooling and crystallization at room temperature.

[0048] The components and contents of the esterification products obtained in step (2) above were analyzed by gas chromatography. The chromatogram of the esterification products is shown below. Figure 2 As shown, the main components are listed in Table 2:

[0049] Table 2. Gas chromatogram of the esterified product prepared in Example 3 of the present invention. Main components.

[0050] Serial Number compound Molecular formula molecular weight content / % 1 α-Pinene <![CDATA[C 10 H 16 ]]> 136 1.241 2 Camphene <![CDATA[C 10 H 16 ]]> 136 6.754 3 α-Terpinene <![CDATA[C 10 H 16 ]]> 136 1.711 4 For cymenes, p-Cymene <![CDATA[C 10 H 14 ]]> 134 2.008 5 d-Limonene <![CDATA[C 10 H 16 ]]> 136 10.218 6 γ-Terpinene <![CDATA[C 10 H 16 ]]> 136 0.867 7 Turpinoene <![CDATA[C 10 H 16 ]]> 136 4.717 8 Fenchyl acetate <![CDATA[C 12 H 20 O2]]> 200 1.843 9 Bornyl formate <![CDATA[C 11 H 18 O2]]> 182 5.361 10 iso-Bornyl formate <![CDATA[C 11 H 18 O2]]> 182 3.064 11 oligomers - - 7.116 12 Difluoromethyl oxalate, DFO <![CDATA[C 22 H 34 O4]]> 362 1.282 13 Borneol oxalate, BFO <![CDATA[C 22 H 34 O4]]> 362 8.703 14 IBFO (Isoborneol Oxalate) <![CDATA[C 22 H 34 O4]]> 362 2.165 15 Di-n-borneol oxalate, DBO <![CDATA[C 22 H 34 O4]]> 362 13.145 16 BIBO isoborneol oxalate <![CDATA[C 22 H 34 O4]]> 362 8.939 17 Diisoborneol oxalate, DIBO <![CDATA[C 22 H 34 O4]]> 362 2.034

[0051] The esterification products contain three monoesters: borneol acetate (FA), n-borneol formate (BF), and isoborneol formate (IBF), and six diesters: diborneol oxalate (DFO), n-borneol oxalate (BFO), isoborneol oxalate (IBFO), di-n-borneol oxalate (DBO), n-borneol oxalate isoborneol oxalate (BIBO), and diisoborneol oxalate (DIBO). The diesters can be represented as twice the corresponding monoesters, i.e., 1DFO = 2FF (FF being borneol formate), 1BFO = 1BF + 1FF, 1IBFO = 1BF + 1IBF, 1DBO = 2BF, 1BIBO = 1BF + 1IBF, and 1DIBO = 2IBF. The calculated yield of borneol monoesters was 45.17%, of which n-borneol oxalate accounted for 40.47% and isoborneol oxalate accounted for 4.34%.

[0052] The borneol synthesized in step (2) was dissolved in ethyl acetate, and the components and contents of the synthesized borneol were analyzed by gas chromatography. The gas chromatogram of the synthesized borneol is shown below. Figure 3 As shown in Table 3, the main components of the synthetic borneol are as follows. The synthetic borneol content is 90.24%, and it does not contain camphor, which meets the national pharmacopoeia standards.

[0053] Table 3. Chromatograms of the main components of the synthetic borneol prepared in Example 3 of the present invention.

[0054] Serial Number compound Molecular formula molecular weight content / % 1 Fenchol <![CDATA[C 10 H 18 O]]> 154 3.40 2 iso-Borneol <![CDATA[C 10 H 18 O]]> 154 6.36 3 Endo-Borneol <![CDATA[C 10 H 18 O]]> 154 90.24

[0055] Example 4

[0056] The refinery solid waste catalyst prepared in Example 1 was used to prepare high-quality borneol. The operation steps are as follows:

[0057] (1) Weigh 35g of turpentine oil (α-pinene content ≥85%) and 9g of anhydrous oxalic acid into a three-necked flask equipped with a stirrer, thermometer and reflux condenser, add 1.5g of the refinery solid waste catalyst HS-SFCC prepared in Example 1, and then carry out the esterification reaction at 95°C for 5h, with the stirring speed at 400r / min during the reaction.

[0058] (2) After the reaction was completed, the esterification product and the catalyst were separated by vacuum filtration to obtain 34g of esterification product. The esterification product was dissolved in 50g of anhydrous ethanol and then 50g of 5% NaOH solution was added. The saponification reaction was carried out at 80℃ for 1h with a stirring speed of 500r / min. After the saponification reaction was completed, the ethanol was removed by rotary evaporation and the borneol was obtained after cooling and crystallization at room temperature.

[0059] The components and contents of the esterification product in step (1) were analyzed by gas chromatography, and the yield of borneol monoester was calculated to be 52.88%, of which the content of n-borneol ester was 44.93% and the content of isoborneol ester was 7.95%. The borneol synthesized in step (2) was dissolved in ethyl acetate, and the components and contents of the synthesized borneol were analyzed by gas chromatography. The main components of the synthesized borneol are shown in Table 6. The content of n-borneol in the synthesized borneol was 85.67%, and it did not contain camphor, which meets the national pharmacopoeia standard.

[0060] Table 6. Chromatograms of the main components of the synthetic borneol prepared in Example 4 of this invention.

[0061] Serial Number compound Molecular formula molecular weight content / % 1 Fenchol <![CDATA[C 10 H 18 O]]> 154 4.77 2 iso-Borneol <![CDATA[C 10 H 18 O]]> 154 9.56 3 Endo-Borneol <![CDATA[C 10 H 18 O]]> 154 85.67

[0062] Example 5

[0063] The refinery solid waste catalyst prepared in Example 1 was used to prepare high-quality borneol. The operation steps are as follows:

[0064] (1) Weigh 35g of turpentine oil (α-pinene content ≥85%) and 9g of anhydrous oxalic acid into a three-necked flask equipped with a stirrer, thermometer and reflux condenser, add 1.5g of the refinery solid waste catalyst HS-SFCC prepared in Example 1, and then carry out the esterification reaction at 105℃ for 4h, with the stirring speed at 400r / min during the reaction.

[0065] (2) After the reaction was completed, the esterification product and the catalyst were separated by vacuum filtration to obtain 34g of esterification product. The esterification product was dissolved in 50g of anhydrous ethanol and then 50g of 5% NaOH solution was added. The saponification reaction was carried out at 80℃ for 1h with a stirring speed of 500r / min. After the saponification reaction was completed, the ethanol was removed by rotary evaporation and the borneol was obtained after cooling and crystallization at room temperature.

[0066] The components and contents of the esterification product in step (1) were analyzed by gas chromatography. The yield of borneol monoester was calculated to be 49.25%, of which n-borneol ester content was 36.48% and isoborneol ester content was 12.77%. The borneol synthesized in step (2) was dissolved in ethyl acetate, and the components and contents of the synthesized borneol were analyzed by gas chromatography. The main components of the synthesized borneol are shown in Table 8. The n-borneol content in the synthesized borneol was 78.42%, and it did not contain camphor, which meets the national pharmacopoeia standard.

[0067] Table 8. Chromatograms of the main components of the synthetic borneol prepared in Example 5 of the present invention.

[0068] Serial Number compound Molecular formula molecular weight content / % 1 Fenchol <![CDATA[C 10 H 18 O]]> 154 7.63 2 iso-Borneol <![CDATA[C 10 H 18 O]]> 154 13.95 3 Endo-Borneol <![CDATA[C 10 H 18 O]]> 154 78.42

[0069] Example 6

[0070] The refinery solid waste catalyst prepared in Example 2 was used to prepare high-quality borneol. The operation steps are as follows:

[0071] In step (1), 1.5g of the refinery solid waste catalyst HS-SFCC prepared in Example 2 was added. The rest of the operation was the same as in Example 4. After cooling and crystallizing at room temperature, camphor was obtained.

[0072] The components and contents of the esterification product in step (1) were analyzed by gas chromatography, and the yield of borneol monoester was calculated to be 49.31%, of which the content of n-borneol ester was 40.06% and the content of isoborneol ester was 9.25%. The borneol synthesized in step (2) was dissolved in ethyl acetate, and the components and contents of the synthesized borneol were analyzed by gas chromatography. The main components of the synthesized borneol are shown in Table 9. The content of n-borneol in the synthesized borneol was 80.49%, and it did not contain camphor, which meets the national pharmacopoeia standard.

[0073] Table 9. Chromatograms of the main components of the synthetic borneol prepared in Example 6 of the present invention.

[0074] Serial Number compound Molecular formula molecular weight content / % 1 Fenchol <![CDATA[C 10 H 18 O]]> 154 5.02 2 iso-Borneol <![CDATA[C 10 H 18 O]]> 154 14.44 3 Endo-Borneol <![CDATA[C 10 H 18 O]]> 154 80.49

[0075] Comparative Example 1

[0076] A method for preparing a catalyst for synthesizing borneol, comprising the following steps:

[0077] Commercially available hydrated titanium dioxide (TiO(OH)2) was used as the catalyst for preparing borneol. In step (1), "add 1.5g of the above-mentioned reserve refinery solid waste catalyst HS-SFCC" was replaced with "add 1.5g of commercially available hydrated titanium dioxide (TiO(OH)2)". The rest of the operation was the same as in Example 1, and the catalyst for synthesizing borneol was prepared.

[0078] Comparative Example 2

[0079] (1) Weigh 35g of turpentine oil (α-pinene content ≥85%) and 9g of anhydrous oxalic acid into a three-necked flask equipped with a stirrer, thermometer and reflux condenser. Add 1.5g of the catalyst for synthesizing camphor prepared in Comparative Example 1. The heating mode is 55℃ for 0.5 hours, 65℃ for 0.5 hours, 75℃ for 0.5 hours, and 85℃ for 3.5 hours. The co-esterification reaction lasts for 4 hours (it was attempted to carry out esterification directly at 85℃, but it was found that the reaction system would produce violent boiling, which posed a great safety hazard. Therefore, the staged heating mode was adopted). The stirring speed during the reaction is 400r / min.

[0080] The remaining operations were the same as in Example 3, and the esterified product synthesized by hydrated titanium dioxide was obtained.

[0081] Gas chromatography was used to analyze the components and contents of the esterification products synthesized using hydrated titanium dioxide as a catalyst. The chromatogram of the esterification products is shown below. Figure 4 As shown, the main components are listed in Table 4:

[0082] Table 4. Gas chromatogram of the esterification product in Comparative Example 2, showing the main components.

[0083]

[0084]

[0085] Calculations showed that the yield of borneol monoester in the esterification product prepared using commercially available hydrated titanium dioxide as a catalyst was 48.51%, with n-borneol ester content of 32.83% and isoborneol ester content of 15.69%. Borneol synthesized using commercially available hydrated titanium dioxide as a catalyst was dissolved in ethyl acetate, and the components and contents of the synthesized borneol were analyzed by gas chromatography. The gas chromatogram of the synthesized borneol is shown below. Figure 5 As shown in Table 5, the main components of the synthetic borneol are as follows. The content of borneol in the synthetic borneol is only 53.31%, which is lower than the national pharmacopoeia standard, and it also contains other impurities.

[0086] Table 5. Chromatograms of borneol synthesized in Comparative Example 2, showing the main components.

[0087] Serial Number compound Molecular formula molecular weight content / % 1 Fenchol <![CDATA[C 10 H 18 O]]> 154 4.91 2 iso-Borneol <![CDATA[C 10 H 18 O]]> 154 34.02 3 Endo-Borneol <![CDATA[C 10 H 18 O]]> 154 53.31

[0088] Comparative Example 3

[0089] (1) Weigh 35g of turpentine oil (α-pinene content ≥85%) and 9g of anhydrous oxalic acid into a three-necked flask equipped with a stirrer, thermometer and reflux condenser. Add 1.5g of the catalyst for synthesizing camphor prepared in Comparative Example 1. The heating mode is 55℃ for 0.5 hours, 65℃ for 0.5 hours, 75℃ for 0.5 hours, 85℃ for 0.5 hours, and 95℃ for 3 hours. The co-esterification reaction lasts for 5 hours (it was attempted to carry out esterification directly at 95℃, but it was found that the reaction system would produce violent boiling, which posed a great safety hazard. Therefore, the staged heating mode was adopted). The stirring speed during the reaction is 400r / min.

[0090] The remaining operations were the same as in Example 4, and the esterified product synthesized by hydrated titanium dioxide was obtained.

[0091] The components and contents of the esterification product synthesized using hydrated titanium dioxide as a catalyst were analyzed by gas chromatography. The yield of borneol monoester prepared using commercially available hydrated titanium dioxide as a catalyst was calculated to be 54.67%, with n-borneol ester content of 36.48% and isoborneol ester content of 18.19%. Borneol synthesized using commercially available hydrated titanium dioxide as a catalyst was dissolved in ethyl acetate, and the components and contents of the synthesized borneol were analyzed by gas chromatography. The main components are shown in Table 7. The n-borneol content in the synthesized borneol was only 50.51%, lower than the national pharmacopoeia standard, and it also contained other impurities.

[0092] Table 7. Chromatograms of borneol synthesized in Comparative Example 3, showing the main components.

[0093] Serial Number compound Molecular formula molecular weight content / % 1 Fenchol <![CDATA[C 10 H 18 O]]> 154 5.91 2 iso-Borneol <![CDATA[C 10 H 18 O]]> 154 35.87 3 Endo-Borneol <![CDATA[C 10 H 18 O]]> 154 50.51

[0094] Comparative Example 4

[0095] (1) Weigh 35g of turpentine oil (α-pinene content ≥85%) and 9g of anhydrous oxalic acid into a three-necked flask equipped with a stirrer, thermometer and reflux condenser. Add 1.5g of the catalyst for synthesizing camphor prepared in Comparative Example 1. The heating mode is 55℃ 0.5h - 65℃ 0.5h - 75℃ 0.5h - 85℃ 0.5h - 95℃ 0.5h - 105℃ 1.5h. The esterification reaction lasts for 4 hours (it was attempted to carry out esterification directly at 105℃, but it was found that the reaction system would produce violent boiling, which posed a great safety hazard. Therefore, the staged heating mode was adopted). The stirring speed during the reaction is 400r / min.

[0096] The remaining operations were the same as in Example 5, and the esterified product synthesized by hydrated titanium dioxide was obtained.

[0097] The components and contents of the esterification product synthesized using hydrated titanium dioxide as a catalyst were analyzed by gas chromatography. The yield of borneol monoester prepared using commercially available hydrated titanium dioxide as a catalyst was calculated to be 58.94%, with n-borneol ester content of 33.28% and isoborneol ester content of 25.66%. Borneol synthesized using commercially available hydrated titanium dioxide as a catalyst was dissolved in ethyl acetate, and the components and contents of the synthesized borneol were analyzed by gas chromatography. The main components are shown in Table 9. The n-borneol content in the synthesized borneol was only 46.82%, which does not meet the national pharmacopoeia standard, and it also contained other impurities.

[0098] Table 9. Chromatograms of the synthesized borneol in Comparative Example 4, showing the main components.

[0099] Serial Number compound Molecular formula molecular weight content / % 1 Fenchol <![CDATA[C 10 H 18 O]]> 154 6.21 2 iso-Borneol <![CDATA[C 10 H 18 O]]> 154 36.10 3 Endo-Borneol <![CDATA[C 10 H 18 O]]> 154 46.82

[0100] Comparative Example 5

[0101] SFCC without sulfuric acid impregnation: Weigh 10g of SFCC and place it in a crucible. Place it in a muffle furnace and calcine at 650℃ for 4 hours to remove the coke deposited in the SFCC. After calcination, grind it through a 160-mesh sieve to obtain SFCC without sulfuric acid impregnation.

[0102] Unimpregnated sulfuric acid SFCC was used as the catalyst for the preparation of borneol.

[0103] In step (1), “add 1.5g of the refinery solid waste catalyst HS-SFCC prepared in Example 1” is replaced with “add 1.5g of SFCC that has not been impregnated with sulfuric acid”. The rest of the operation is the same as in Example 3, and borneol is obtained.

[0104] The components and contents of the esterification products synthesized using SFCC without sulfuric acid impregnation were analyzed by gas chromatography. Calculations showed that the conversion rate of α-pinene in the esterification reaction using SFCC without sulfuric acid impregnation as a catalyst was only 26.18%, and the yield of borneol monoester in the prepared esterification product was 7.61%, with n-borneol ester content of 7.42% and isoborneol ester content of 0.19%. Borneol synthesized using SFCC without sulfuric acid impregnation as a catalyst was dissolved in ethyl acetate, and the components and contents of the synthesized borneol were analyzed by gas chromatography. The main components are shown in Table 10. The n-borneol content in the synthesized borneol was 93.21%, which meets the national pharmacopoeia standard, but the borneol yield was too low.

[0105] Table 10 shows the chromatograms of the synthesized borneol in Comparative Example 5, including a table of the main components.

[0106] Serial Number compound Molecular formula molecular weight content / % 1 iso-Borneol <![CDATA[C 10 H 18 O]]> 154 3.25 2 Endo-Borneol <![CDATA[C 10 H 18 O]]> 154 93.21

[0107] Comparative Example 6

[0108] A method for preparing a catalyst from solid waste from an oil refinery, comprising the following steps:

[0109] (ii) Take 10g of SFCC obtained after sieving in step (i), mix it with 40g of sulfuric acid solution with a concentration of 4mol / L, and impregnate it in a water bath at 50℃ with a stirring speed of 150r / min for 12h. After impregnation, centrifuge and filter to remove the extraction solution and take the filter residue.

[0110] The remaining operations are the same as in Example 1, and refinery solid waste catalyst A is obtained.

[0111] The following are the operational steps for preparing high-quality borneol using the above-mentioned refinery solid waste catalyst A:

[0112] In step (1), “add 1.5g of the refinery solid waste catalyst HS-SFCC prepared in Example 1” is replaced with “add 1.5g of refinery solid waste catalyst A”. The rest of the operation is the same as in Example 3, and borneol is obtained.

[0113] The components and contents of the esterification product in step (1) were analyzed by gas chromatography. The conversion rate of α-pinene was 93.93%, and the yield of borneol monoester was calculated to be 40.22%, of which the content of n-borneol ester was 36.37% and the content of isoborneol ester was 3.85%. The borneol synthesized in step (2) was dissolved in ethyl acetate, and the components and contents of the synthesized borneol were analyzed by gas chromatography. The main components of the synthesized borneol are shown in Table 11. The content of n-borneol in the synthesized borneol was 77.04%, and it did not contain camphor, which meets the national pharmacopoeia standard.

[0114] Table 11 Chromatograms of the Synthetic Borneol in Comparative Example 6: Main Components

[0115] Serial Number compound Molecular formula molecular weight content / % 1 Fenchol <![CDATA[C 10 H 18 O]]> 154 3.65 2 iso-Borneol <![CDATA[C 10 H 18 O]]> 154 19.26 3 Endo-Borneol <![CDATA[C 10 H 18 O]]> 154 77.04

[0116] Comparative Example 7

[0117] A method for preparing a catalyst from solid waste from an oil refinery, comprising the following steps:

[0118] (ii) Take 10g of SFCC obtained after sieving in step (i), mix it with 40g of sulfuric acid solution with a concentration of 0.5mol / L, and impregnate it in a water bath at 50℃ with a stirring speed of 150r / min for 12h. After impregnation, centrifuge and filter to remove the extraction solution, and take the filter residue.

[0119] The remaining operations are the same as in Example 1, to obtain refinery solid waste catalyst B.

[0120] The following are the operational steps for preparing high-quality borneol using the above-mentioned refinery solid waste catalyst B:

[0121] In step (1), “add 1.5g of the refinery solid waste catalyst HS-SFCC prepared in Example 1” is replaced with “add 1.5g of refinery solid waste catalyst B”. The rest of the operation is the same as in Example 3, and borneol is obtained.

[0122] The components and contents of the esterification product in step (1) were analyzed by gas chromatography. The conversion rate of α-pinene was 94.75%, and the yield of borneol monoester was calculated to be 27.87%, of which the content of n-borneol ester was 24.82% and the content of isoborneol ester was 3.05%. The borneol synthesized in step (2) was dissolved in ethyl acetate, and the components and contents of the synthesized borneol were analyzed by gas chromatography. The main components of the synthesized borneol are shown in Table 12. The content of n-borneol in the synthesized borneol was 87.62%, and it did not contain camphor, which meets the national pharmacopoeia standard.

[0123] Table 12 Chromatograms of Synthetic Borneol in Comparative Example 7: Main Components

[0124] Serial Number compound Molecular formula molecular weight content / % 1 Fenchol <![CDATA[C 10 H 18 O]]> 154 2.62 2 iso-Borneol <![CDATA[C 10 H 18 O]]> 154 9.76 3 Endo-Borneol <![CDATA[C 10 H 18 O]]> 154 87.62

[0125] The foregoing description of specific exemplary embodiments of the invention is for illustrative and explanatory purposes. These descriptions are not intended to limit the invention to the precise forms disclosed, and it will be apparent that many changes and variations can be made in accordance with the foregoing teachings. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application, thereby enabling those skilled in the art to implement and utilize various different exemplary embodiments of the invention, as well as various different choices and variations. The scope of the invention is intended to be defined by the claims and their equivalents.

Claims

1. The application of a catalyst made from solid waste from an oil refinery in the preparation of borneol, characterized in that: The refinery solid waste catalyst uses refinery solid waste SFCC as raw material, and after roasting, impregnation and roasting, a refinery solid waste catalyst HS-SFCC with suitable number, intensity and distribution of Brønsted and Lewis acid sites is obtained; the refinery solid waste SFCC is a refinery solid waste fluidized catalytic cracking catalyst. The method for preparing the catalyst from solid waste of the refinery includes the following steps: (i) Roast refinery solid waste at 450~650 °C for 4~6 h; (ii) Impregnate the SFCC obtained after calcination in step (i) with a sulfuric acid solution of concentration of 1~2 mol / L in a water bath at 25~75 ℃, according to a liquid-to-solid mass ratio of 1~5, for 6~12 h, filter after impregnation, and take the filter residue; (iii) After the filter residue obtained in the washing step (ii) is brought to a pH of 6-7, the washed material is calcined at 350-750 °C for 2-7 h to obtain sulfuric acid modified refinery solid waste HS-SFCC, which is the refinery solid waste catalyst.

2. The application of the refinery solid waste catalyst according to claim 1 in the preparation of camphor, characterized in that: In step (i), the solid waste SFCC from the oil refinery is roasted at 650 °C for 4 h; in step (iii), the material obtained after washing is roasted at 550 °C for 4 h.

3. The application of the refinery solid waste catalyst according to claim 1 in the preparation of camphor, characterized in that: In step (ii), the liquid-solid mass ratio of the SFCC obtained after calcination in step (i) to the sulfuric acid solution is 4.

4. The application of the refinery solid waste catalyst according to claim 1 in the preparation of camphor, wherein the application comprises the following steps: (1) Add the solid waste catalyst from the refinery to turpentine and oxalic acid. The amount of catalyst added is 3% to 7% of the total mass of turpentine and anhydrous oxalic acid. Then carry out the esterification reaction at 55 to 105 °C for 2 to 7 h. During the reaction, the stirring speed is 200 r / min to 600 r / min. (2) After the reaction is completed, the product is filtered under reduced pressure and dissolved in anhydrous ethanol. Then sodium hydroxide solution is added to carry out the saponification reaction. During the reaction, the stirring speed is 500 r / min to 600 r / min. After the reaction is completed, the product is evaporated, cooled and crystallized to obtain borneol.

5. The application of the refinery solid waste catalyst according to claim 4 in the preparation of camphor, characterized in that: The turpentine oil mentioned in step (1) is turpentine oil with an α-pinene content ≥85%; the molar ratio of turpentine oil to anhydrous oxalic acid is 1:0.2~0.

7.

6. The application of the refinery solid waste catalyst according to claim 5 in the preparation of camphor, characterized in that: The molar ratio of turpentine oil to anhydrous oxalic acid is 1:0.

5.

7. The application of the refinery solid waste catalyst according to claim 4 in the preparation of camphor, characterized in that: In step (2), the mass concentration of sodium hydroxide solution is 3%~5%; the mass ratio of esterification product to sodium hydroxide solution in step (2) is 1:1~2.

8. The application of the refinery solid waste catalyst according to claim 4 in the preparation of camphor, characterized in that: The saponification reaction described in step (2) is carried out at 80 °C for 1 h.

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