Catalyst for solid waste of oil refinery as well as preparation method and application of catalyst

Abstract

The invention discloses an oil refinery solid waste catalyst which is characterized in that oil refinery solid waste SFCC is used as a raw material, and the oil refinery solid waste catalyst HS-SFCC with proper number, strength and distribution of # imgabs0 and Lewis acid sites is obtained after roasting, dipping and roasting. According to the present invention, the oil refinery solid waste is utilized to catalyze the turpentine to synthesize the high value-added borneol, such that the harmlessness and the recycling of the oil refinery solid waste can be achieved, the conversion of the turpentine to the high value-added product can be achieved, and the production technology with the high economic benefit is provided for the synthesis of the borneol from the turpentine.

Description

Technical Field

[0001] The invention relates to the regeneration and modification of heavy oil catalytic cracking solid waste in the petrochemical industry and the application in the field of fine processing of turpentine to produce high value-added products, and specifically to a catalyst for solid waste from an oil refinery and a preparation method and application thereof. Background Art

[0002] Turpentine is a colorless to light yellow transparent natural organic compound with a unique rosin smell. It is mainly extracted by rosin steam distillation and pine wood pine seed solvent extraction. It can be divided into gum turpentine, wood turpentine, sulfate turpentine and distilled turpentine. Turpentine generally refers to gum turpentine in my country. my country is rich in turpentine resources, so my country mainly produces gum turpentine, with an annual output of 90,000 to 110,000 tons of turpentine. The production areas are mainly concentrated in Yunnan, Guangxi, Guangdong and other places. Turpentine is composed of a mixture of terpenes, mainly including monoterpenes such as α-pinene and β-pinene, limonene, camphene and terpinene. The national standard GB / T12901-2006 "Gum Turpentine" stipulates that turpentine with a pinene content greater than 85% is a superior turpentine. Turpentine is the world's largest essential oil with a wide range of uses and extremely high cost performance. It is used in many fields such as medicine, spices, and agriculture, and is vividly called "oil in trees." As a low-cost and abundant biomass resource, turpentine can be converted into high-value-added chemicals, which has feasibility and great commercial prospects. α-pinene is the main component of turpentine and is the raw material for synthesizing fine chemicals such as camphor, spices, turpentine alcohol, terpene resins and borneol.

[0003] Turpentine oil can be synthesized into high value-added product borneol through esterification-saponification reaction. Borneol has anti-inflammatory, analgesic, antipyretic, antibacterial, nerve protection and penetration promoting effects, and is widely used in medicine, food, daily necessities and other fields. The 2020 edition of the Chinese Pharmacopoeia stipulates that borneol (C 10 H 18 O) content shall not be less than 55%, camphor (C 10 H 16 O) content shall not exceed 0.50%. Synthetic borneol can be divided into orthoborneol with an inward configuration and isoborneol with an extroverted configuration according to the spatial structure, among which isoborneol has a greater irritation to the gastric mucosa and a stronger hepatotoxicity, and has certain side effects. Therefore, in the process of synthesizing borneol, it is more inclined to obtain high-quality borneol with a higher content of orthoborneol.

[0004] The methods for synthesizing borneol include camphor reduction method, organomagnesium compound decomposition method, biosynthesis method, α-pinene direct hydration method, and α-pinene esterification-saponification method. At present, the industry mainly uses the two-step esterification-saponification method to produce borneol, that is, α-pinene and anhydrous oxalic acid are used as raw materials, and an esterification reaction is carried out under the action of catalysts such as boric anhydride, metaboric acid and metatitanic acid to produce borneol; oxalic acid is then hydrolyzed and saponified with alkali solution to produce borneol. The key to this synthetic route is the selection of catalysts in the esterification reaction of α-pinene. The use of catalysts such as boric anhydride, metaboric acid and metatitanic acid will lead to violent reactions, difficult control, and difficult recovery of catalysts, and high requirements for reaction equipment and low raw material utilization. Therefore, it is imperative to develop environmentally friendly and efficient catalysts. Sulfuric acid, hydrochloric acid, etc. can be used as liquid catalysts for the esterification reaction of α-pinene. Although they have high catalytic activity, the catalyst is not easy to separate after the reaction, and the liquid acid will corrode the reaction equipment, thereby hindering its industrial application. Solid acid catalysts mainly include boron-containing, titanium-containing, sulfonic acid-containing, boron-titanium composite, noble metal and solid superacid catalysts. These catalysts can be quickly separated from the product, but there are still disadvantages such as complex catalyst preparation process, long time consumption, short life, difficult reaction control, and too high isoborneol content in the product borneol, which makes the production efficiency of borneol low. At present, ionic liquids are introduced into the synthetic borneol system as an environmentally friendly catalyst with good catalytic activity. However, ionic liquids need to cooperate with chloroacetic acid to form a composite catalytic system, and chloroacetic acid has certain dangers, so it is not conducive to the industrial application of such catalysts.

[0005] Fluid 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, V, coke and alkali metals continues to increase, resulting in reduced 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. They have been included in the National List of Hazardous Wastes since August 1, 2016. In the early days, the traditional landfill treatment of SFCC not only caused pollution of soil and water resources, but also led to a large amount of waste of effective resources. SFCC contains not only national strategic resources such as Ni, V, La, Ce, but also rich silicon and aluminum elements. The zeolite molecular sieve and Al2O3 matrix it mainly contains have a large number of micropores and specific surface areas. Therefore, it is urgent to treat SFCC harmlessly and recycle it. Summary of the invention

[0006] In order to solve the above technical problems, a catalyst of solid waste from an oil refinery is used to prepare high-quality borneol. The raw materials used are turpentine and anhydrous oxalic acid, thereby obtaining a method for preparing high-quality borneol with low cost, short reaction time, simpler operation and safety.

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

[0008] A refinery solid waste catalyst, which uses refinery solid waste SFCC as raw material, and is obtained after roasting, impregnation and roasting. and refinery solid waste catalyst HS-SFCC with suitable number, strength and distribution of Lewis acid sites.

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

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

[0011] (ii) impregnating the SFCC obtained after calcination in step (i) with a sulfuric acid solution having a concentration of 1 to 2 mol / L in a water bath at 25 to 75° C. at a liquid-to-solid mass ratio of 1 to 5 for 6 to 12 hours, and after impregnation, centrifugally separating and filtering to remove the leaching solution and obtain a filter residue;

[0012] (iii) washing the filter residue obtained after filtering in step (ii) with deionized water until the pH value is 6-7, and calcining the washed material in a muffle furnace at 350-750° C. for 2-7 hours to obtain a refinery solid waste HS-SFCC modified with sulfuric acid, i.e., a refinery solid waste catalyst.

[0013] Preferably, in step (i), the refinery solid waste SFCC is calcined in a muffle furnace at 650° C. for 4 h; and in step (iii), the washed material is calcined in a muffle furnace at 550° C. for 4 h.

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

[0015] Application of the solid waste catalyst from an oil refinery prepared as above in the preparation of high-quality borneol;

[0016] The application includes the following steps:

[0017] (1) adding the solid waste catalyst from the oil refinery to turpentine and anhydrous oxalic acid, wherein the catalyst addition amount is 3% to 7% of the total mass of the turpentine and anhydrous oxalic acid, and then performing an esterification reaction at 55 to 105° C. for 2 to 7 hours, and 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, and the esterification product is dissolved in 20 to 50 g of anhydrous ethanol, and then sodium hydroxide solution is added to carry out saponification reaction. The stirring speed during the reaction is 500 r / min to 600 r / min. After the reaction is completed, the ethanol is removed by rotary evaporation, and borneol is obtained after cooling and crystallization at room temperature.

[0019] Preferably, the turpentine oil described in step (1) is turpentine oil with an α-pinene content of ≥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 preferably the molar ratio of turpentine oil to anhydrous oxalic acid is 1:0.5.

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

[0022] Compared with the prior art, the present invention has the following beneficial effects:

[0023] (1) The catalyst of the present invention is obtained by impregnation with sulfuric acid of a specific concentration. By using HS-SFCC with appropriate number, strength and distribution of Lewis acid sites and optimized calcination time, a catalyst with high reactivity and selectivity for catalyzing the synthesis of borneol from turpentine oil was obtained;

[0024] (2) The present invention uses turpentine and anhydrous oxalic acid as raw materials, and uses modified refinery solid waste HS-SFCC as a catalyst, and utilizes the high specific surface area, multi-level 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 and the selectivity for n-borneol ester, thereby realizing the synthesis of high-quality borneol and the directional conversion of turpentine to high-quality borneol;

[0025] (3) The present invention utilizes solid waste from refineries to catalyze turpentine oil to synthesize high-value-added borneol, which can not only achieve the harmlessness and resource utilization of solid waste from refineries, but also realize the conversion of turpentine oil into high-value-added products, providing a more economically efficient production technology for synthesizing borneol from turpentine oil. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] Figure 1 The gas chromatogram of the raw material turpentine oil used in the present invention.

[0027] Figure 2 The gas chromatogram of the esterification 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 esterification product synthesized in Comparative Example 2 is shown in FIG.

[0030] Figure 5 This is the gas chromatogram of the synthetic borneol prepared in Comparative Example 2. DETAILED DESCRIPTION

[0031] The specific implementation method is described in detail below in conjunction with the accompanying drawings, but it should be understood that the scope of protection of the present invention is not limited by the specific implementation method. The raw materials and reagents used in the examples are all commercially available unless otherwise specified. The three-necked flask used in the implementation is equipped with an agitator, a thermometer and a condensing reflux device. The anhydrous oxalic acid used in the examples was purchased from Shanghai McLean Biochemical Technology Co., Ltd. The solid waste from the refinery, namely the waste fluid catalytic cracking catalyst (SFCC for short), was provided by PetroChina Guangxi Tiandong Petrochemical General Plant Co., Ltd. Turpentine was provided by Guangxi Richeng Forest Products Chemical Co., Ltd. The turpentine was subjected to gas chromatography detection, and the resulting gas chromatogram is shown as follows Figure 1 The main components are shown in Table 1.

[0032] Table 1 Main components of the gas chromatogram of the raw material turpentine oil used in the present 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 p-Cymene <![CDATA[C 10 H 14 ]]> 134 4.59 5 Limonene, d-Limonene <![CDATA[C 10 H 16 ]]> 136 3.17

[0034] GC conditions (gas chromatography conditions): Agilent 7820A gas chromatograph was used, the chromatographic column was HP-5MS (30m×0.25mm×0.25μm) capillary column, detector: hydrogen ion flame detector, carrier gas: high-purity nitrogen, fuel gas: high-purity hydrogen, auxiliary gas: air, detector temperature: 280°C, column head pressure 70KPa, split ratio: 50:1, injection volume: 0.4μL, flow rate: 60mL / min.

[0035] Example 1

[0036] A method for preparing a catalyst from solid waste from an oil refinery, the operating steps are as follows:

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

[0038] (ii) taking 10 g of the SFCC obtained after sieving in step (i), mixing it with 40 g of a 1 mol / L sulfuric acid solution, and immersing it in a water bath at 50° C. at a stirring speed of 150 r / min for 12 h. After immersion, centrifugation and filtration were performed to remove the leaching solution and obtain the filter residue;

[0039] (iii) washing the filter residue obtained after filtering in step (ii) with deionized water until the pH value is 6-7, and calcining the washed material in a muffle furnace at 550° C. for 4 h to obtain the refinery solid waste HS-SFCC modified with sulfuric acid, i.e., the refinery solid waste catalyst, which is crushed through a 160-mesh sieve for later use.

[0040] Example 2

[0041] A method for preparing a catalyst from solid waste from an oil refinery, the operating steps are as follows:

[0042] (ii) taking 10 g of the SFCC obtained after sieving in step (i), mixing it with 40 g of a 2 mol / L sulfuric acid solution, and impregnating it in a water bath at 50° C. at a stirring speed of 150 r / min for 12 h. After impregnation, centrifugation and filtration were performed to remove the leaching solution and obtain a filter residue;

[0043] The remaining operations were the same as those in Example 1 to obtain a refinery solid waste catalyst.

[0044] Example 3

[0045] The refinery solid waste catalyst prepared in Example 1 was used to prepare high-quality borneol, and the operating steps were as follows:

[0046] (1) 35 g of turpentine (α-pinene content ≥ 85%) and 9 g of anhydrous oxalic acid were weighed and put into a three-necked flask equipped with a stirrer, a thermometer and a condensing reflux device, and 1.5 g of the spare refinery solid waste catalyst HS-SFCC in Example 1 was added, and then an esterification reaction was carried out at 85° C. for 4 h, and the stirring speed during the reaction was 400 r / min;

[0047] (2) After the reaction, the esterification product and the catalyst were separated by vacuum filtration to obtain 34 g of the esterification product. The esterification product was dissolved in 50 g of anhydrous ethanol, and then 50 g of a 5% NaOH solution was added. The saponification reaction was carried out at 80° C. for 1 h with a stirring speed of 500 r / min. After the saponification reaction, 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 product obtained in the above step (2) were analyzed by gas chromatography. The chromatogram of the esterification product is as follows: Figure 2 The main components are shown in Table 2:

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

[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 p-Cymene <![CDATA[C 10 H 14 ]]> 134 2.008 5 Limonene, 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 Oligomer - - 7.116 12 Difenchyl Oxalate, DFO <![CDATA[C 22 H 34 O4]]> 362 1.282 13 Bornylfenchol oxalate, BFO <![CDATA[C 22 H 34 O4]]> 362 8.703 14 Isoborneolfenyl oxalate, IBFO <![CDATA[C 22 H 34 O4]]> 362 2.165 15 Di-n-bornyl oxalate, DBO <![CDATA[C 22 H 34 O4]]> 362 13.145 16 Bornyl isoborneol oxalate, BIBO <![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 product contains three monoesters, namely, fenchyl acetate (FA), borneol formate (BF), and isoborneol formate (IBF), and six diesters, namely, diborneol oxalate (DFO), borneol oxalate (BFO), isoborneol oxalate (IBFO), diborneol oxalate (DBO), borneol isoborneol oxalate (BIBO), and diisoborneol oxalate (DIBO). The diester can be expressed as twice the corresponding monoester, namely, 1DFO=2FF (FF is fenchyl formate), 1BFO=1BF+1FF, 1IBFO=1BF+1IBF, 1DBO=2BF, 1BIBO=1BF+1IBF, 1DIBO=2IBF, and the calculated yield of borneol monoester is 45.17%, of which the content of borneol ester is 40.47% and the content of isoborneol ester is 4.34%.

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

[0053] Table 3. Chromatogram of main components of 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, and the operating steps were as follows:

[0057] (1) 35 g of turpentine (α-pinene content ≥ 85%) and 9 g of anhydrous oxalic acid were weighed and put into a three-necked flask equipped with a stirrer, a thermometer and a condensing reflux device, and 1.5 g of the refinery solid waste catalyst HS-SFCC prepared in Example 1 was added, and then an esterification reaction was carried out at 95° C. for 5 h. During the reaction, the stirring speed was 400 r / min;

[0058] (2) After the reaction, the esterification product and the catalyst were separated by vacuum filtration to obtain 34 g of the esterification product. The esterification product was dissolved in 50 g of anhydrous ethanol, and then 50 g of a 5% NaOH solution was added. The saponification reaction was carried out at 80° C. for 1 h with a stirring speed of 500 r / min. After the saponification reaction, 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 the above step (1) were analyzed by gas chromatography, and the yield of borneol monoester was calculated to be 52.88%, wherein 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 in the synthetic borneol were analyzed by gas chromatography. The main components of the synthetic borneol are shown in Table 6. The content of n-borneol in the synthetic borneol is 85.67%, and it does not contain camphor, which meets the national pharmacopoeia standard.

[0060] Table 6. Chromatogram of the main components of the synthetic borneol prepared in Example 4 of the present 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, and the operating steps were as follows:

[0064] (1) 35 g of turpentine (α-pinene content ≥ 85%) and 9 g of anhydrous oxalic acid were weighed and put into a three-necked flask equipped with a stirrer, a thermometer and a condensing reflux device, and 1.5 g of the spare refinery solid waste catalyst HS-SFCC in Example 1 was added, and then an esterification reaction was carried out at 105° C. for 4 h. During the reaction, the stirring speed was 400 r / min;

[0065] (2) After the reaction, the esterification product and the catalyst were separated by vacuum filtration to obtain 34 g of the esterification product. The esterification product was dissolved in 50 g of anhydrous ethanol, and then 50 g of a 5% NaOH solution was added. The saponification reaction was carried out at 80° C. for 1 h with a stirring speed of 500 r / min. After the saponification reaction, 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 the above step (1) were analyzed by gas chromatography, and the yield of borneol monoester was calculated to be 49.25%, wherein the content of n-borneol ester was 36.48% and the content of isoborneol ester was 12.77%. The borneol synthesized in step (2) was dissolved in ethyl acetate, and the components and contents in the synthetic borneol were analyzed by gas chromatography. The main components of the synthetic borneol are shown in Table 8. The content of n-borneol in the synthetic borneol is 78.42%, and it does not contain camphor, which meets the national pharmacopoeia standard.

[0067] Table 8. Chromatogram 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, and the operating steps were as follows:

[0071] In step (1), 1.5 g of the spare refinery solid waste catalyst HS-SFCC prepared in Example 2 was added, and the remaining operations were the same as in Example 4. Borneol was obtained after cooling and crystallization at room temperature.

[0072] The components and contents of the esterified product in the above step (1) were analyzed by gas chromatography, and the yield of borneol monoester was calculated to be 49.31%, wherein 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 in the synthetic borneol were analyzed by gas chromatography. The main components of the synthetic borneol are shown in Table 9. The content of n-borneol in the synthetic borneol is 80.49%, and it does not contain camphor, which meets the national pharmacopoeia standard.

[0073] Table 9. Chromatogram 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, the operating steps are as follows:

[0077] Commercially available hydrated titanium dioxide (TiO(OH)2) was used as a catalyst for preparing borneol. In step (1), "add 1.5 g of the above-mentioned spare refinery solid waste catalyst HS-SFCC" was replaced with "add 1.5 g of commercially available hydrated titanium dioxide (TiO(OH)2)", and the remaining operations were the same as in Example 1 to prepare a catalyst for synthesizing borneol.

[0078] Comparative Example 2

[0079] (1) 35 g of turpentine (α-pinene content ≥ 85%) and 9 g of anhydrous oxalic acid were weighed and put into a three-necked flask equipped with a stirrer, a thermometer and a condensation reflux device, and 1.5 g of the catalyst prepared in Comparative Example 1 for synthesized borneol was added. The heating mode was 55° C. for 0.5 hour—65° C. for 0.5 hour—75° C. for 0.5 hour—85° C. for 3.5 hours, and the total esterification reaction was performed for 4 hours (an attempt was made to directly perform esterification at 85° C., but it was found that the reaction system would produce violent boiling phenomenon, which posed a great safety hazard, so a stage heating mode was adopted). During the reaction, the stirring speed was 400 r / min;

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

[0081] Gas chromatography was used to analyze the components and contents of the esterification products synthesized by hydrated titanium dioxide catalysis. The chromatogram of the esterification products is shown in FIG. Figure 4 The main components are shown in Table 4:

[0082] Table 4. is the main component table of the gas chromatogram of the esterification product of Comparative Example 2

[0083]

[0084]

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

[0086] Table 5. Chromatogram of the main components of the synthetic borneol in Comparative Example 2

[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) 35 g of turpentine (α-pinene content ≥ 85%) and 9 g of anhydrous oxalic acid were weighed and put into a three-necked flask equipped with a stirrer, a thermometer and a condensation reflux device, and 1.5 g of the catalyst prepared in Comparative Example 1 for synthesized borneol was added. The heating mode was 55° C. for 0.5 hour—65° C. for 0.5 hour—75° C. for 0.5 hour—85° C. for 0.5 hour—95° C. for 3 hours, and the total esterification reaction was performed for 5 hours (an attempt was made to directly perform esterification at 95° C., but it was found that the reaction system would produce violent boiling phenomenon, which posed a great safety hazard, so a stage heating mode was adopted). During the reaction, the stirring speed was 400 r / min;

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

[0091] Gas chromatography was used to analyze the components and contents of the esterification product synthesized by hydrated titanium dioxide. It was calculated that the yield of borneol monoester in the esterification product prepared by commercially available hydrated titanium dioxide as a catalyst was 54.67%, of which the content of normal borneol ester was 36.48% and the content of isoborneol ester was 18.19%. Borneol synthesized by commercially available hydrated titanium dioxide as a catalyst was dissolved in ethyl acetate, and the components and contents in the synthetic borneol were analyzed by gas chromatography. The main component table is shown in Table 7. The content of normal borneol in the synthetic borneol is only 50.51%, which is lower than the national pharmacopoeia standard, and contains other impurities.

[0092] Table 7. Chromatogram of the main components of the synthetic borneol of Comparative Example 3

[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) 35 g of turpentine (with α-pinene content ≥ 85%) and 9 g of anhydrous oxalic acid were weighed and put into a three-necked flask equipped with a stirrer, a thermometer and a condensation reflux device, and 1.5 g of the catalyst prepared in Comparative Example 1 for synthesized borneol was added. The heating mode was 55° C. for 0.5 hour—65° C. for 0.5 hour—75° C. for 0.5 hour—85° C. for 0.5 hour—95° C. for 0.5 hour—105° C. for 1.5 hour. The esterification reaction lasted for 4 hours (an attempt was made to carry out the esterification directly at 105° C., but it was found that the reaction system would produce violent boiling phenomenon, which posed a great safety hazard, so a stage heating mode was adopted). During the reaction, the stirring speed was 400 r / min;

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

[0097] Gas chromatography was used to analyze the components and contents of the esterification product synthesized by hydrated titanium dioxide. It was calculated that the yield of borneol monoester in the esterification product prepared by commercially available hydrated titanium dioxide as a catalyst was 58.94%, of which the content of borneol ester was 33.28% and the content of isoborneol ester was 25.66%. Borneol synthesized by commercially available hydrated titanium dioxide as a catalyst was dissolved in ethyl acetate, and the components and contents in the synthetic borneol were analyzed by gas chromatography. The main component table is shown in Table 9. The content of borneol in the synthetic borneol is only 46.82%, which does not meet the national pharmacopoeia standards and contains other impurities.

[0098] Table 9. Chromatogram of the main components of the synthetic borneol in Comparative Example 4

[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 not impregnated with sulfuric acid: Weigh 10g of SFCC and place it in a crucible, then place it in a muffle furnace and roast it at 650℃ for 4h to remove the coke deposited in the SFCC. After roasting, grind it through a 160-mesh sieve to obtain SFCC not impregnated with sulfuric acid.

[0102] SFCC not impregnated with sulfuric acid was used as a catalyst for preparing borneol:

[0103] In step (1), "add 1.5 g of the spare refinery solid waste catalyst HS-SFCC prepared in Example 1" is replaced by "add 1.5 g of SFCC that has not been impregnated with sulfuric acid", and the remaining operations are the same as in Example 3 to obtain borneol.

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

[0105] Table 10 is a chromatogram of the main components of the synthetic borneol in Comparative Example 5

[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, the operating steps are as follows:

[0109] (ii) taking 10 g of the SFCC obtained after sieving in step (i), mixing it with 40 g of a 4 mol / L sulfuric acid solution, and immersing it in a water bath at 50° C. at a stirring speed of 150 r / min for 12 h. After immersion, centrifugation and filtration were performed to remove the leaching solution and obtain a filter residue;

[0110] The remaining operations were the same as those in Example 1 to obtain refinery solid waste catalyst A.

[0111] The above-obtained solid waste catalyst A from the refinery is used to prepare high-quality borneol, and the operation steps are as follows:

[0112] In step (1), "add 1.5 g of the refinery solid waste catalyst HS-SFCC prepared in Example 1" is replaced by "add 1.5 g of refinery solid waste catalyst A", and the remaining operations are the same as in Example 3 to obtain borneol.

[0113] The components and contents of the esterified product in the above step (1) were analyzed by gas chromatography. The conversion rate of α-pinene was 93.93%. The yield of borneol monoester was calculated to be 40.22%, wherein 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 in the synthetic borneol were analyzed by gas chromatography. The main components of the synthetic borneol are shown in Table 11. The content of n-borneol in the synthetic borneol was 77.04%, and it did not contain camphor, which met the national pharmacopoeia standards.

[0114] Table 11 Chromatogram of the main components of the synthetic borneol in Comparative Example 6

[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, the operating steps are as follows:

[0118] (ii) taking 10 g of the SFCC obtained after sieving in step (i), mixing it with 40 g of a 0.5 mol / L sulfuric acid solution, and impregnating it in a water bath at 50° C. at a stirring speed of 150 r / min for 12 h. After impregnation, centrifugation and filtration were performed to remove the leaching solution and obtain the filter residue;

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

[0120] The above-obtained solid waste catalyst B from the refinery is used to prepare high-quality borneol, and the operation steps are as follows:

[0121] In step (1), "add 1.5 g of the refinery solid waste catalyst HS-SFCC prepared in Example 1" is replaced with "add 1.5 g of the refinery solid waste catalyst B", and the remaining operations are the same as in Example 3 to obtain borneol.

[0122] The components and contents of the esterified product in the above step (1) were analyzed by gas chromatography. The conversion rate of α-pinene was 94.75%. The yield of borneol monoester was calculated to be 27.87%, wherein 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 in the synthetic borneol were analyzed by gas chromatography. The main components of the synthetic borneol are shown in Table 12. The content of n-borneol in the synthetic borneol was 87.62%, and it did not contain camphor, which met the national pharmacopoeia standards.

[0123] Table 12 Chromatogram of the main components of the synthetic borneol in Comparative Example 7

[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 present invention is for the purpose of illustration and demonstration. These descriptions are not intended to limit the present invention to the precise form disclosed, and it is clear that many changes and variations can be made based on the above teachings. The purpose of selecting and describing the exemplary embodiments is to explain the specific principles of the present invention and its practical application, so that those skilled in the art can realize and utilize various different exemplary embodiments of the present invention and various different selections and changes. The scope of the present invention is intended to be limited by the claims and their equivalents.

Claims

1. A refinery solid waste catalyst, characterized in that: Using SFCC, a solid waste from an oil refinery, as raw material, it is obtained through roasting, impregnation and roasting. and refinery solid waste catalyst HS-SFCC with suitable number, strength and distribution of Lewis acid sites.

2. The method for preparing a catalyst from solid waste from an oil refinery according to claim 1, characterized in that: The following steps are included: (i) calcining the solid waste SFCC from the refinery at 450-650°C for 4-6 hours; (ii) impregnating the SFCC obtained after calcination in step (i) with a sulfuric acid solution having a concentration of 1 to 2 mol / L in a water bath at 25 to 75° C. at a liquid-to-solid mass ratio of 1 to 5 for 6 to 12 hours, filtering after impregnation, and collecting the filter residue; (iii) washing the filter residue obtained after filtering in step (ii) to a pH of 6 to 7, and calcining the washed material at 350 to 750° C. for 2 to 7 hours to obtain a refinery solid waste HS-SFCC modified with sulfuric acid, i.e., a refinery solid waste catalyst.

3. The method for preparing a catalyst from solid waste from an oil refinery according to claim 2, characterized in that: In step (i), the solid waste SFCC from the refinery is roasted at 650° C. for 4 hours; and in step (iii), the washed material is roasted at 550° C. for 4 hours.

4. The method for preparing a catalyst from solid waste from an oil refinery according to claim 2, characterized in that: In step (ii), the solid-to-liquid ratio of the SFCC obtained after calcination in step (i) to the sulfuric acid solution is 1:

4.

5. Use of the refinery solid waste catalyst as claimed in any one of claims 1 to 4 in the preparation of borneol.

6. The use of the solid waste catalyst from an oil refinery in the preparation of borneol according to claim 5, characterized in that: The following steps are included: (1) adding the solid waste catalyst from the refinery to turpentine and oxalic acid, wherein the catalyst addition amount is 3% to 7% of the total mass of the turpentine and anhydrous oxalic acid, and then performing an esterification reaction at 55 to 105° C. for 2 to 7 hours, and the stirring speed during the reaction is 200 r / min to 600 r / min; (2) After the reaction is completed, the product is filtered under reduced pressure, dissolved in anhydrous ethanol, and then sodium hydroxide solution is added to carry out saponification reaction. The stirring speed during the reaction is 500 r / min to 600 r / min. After the reaction is completed, the product is evaporated and cooled and crystallized to obtain borneol.

7. The use of the solid waste catalyst from an oil refinery in the preparation of borneol according to claim 6, characterized in that: The turpentine oil described in step (1) is turpentine oil with an α-pinene content of ≥85%; the molar ratio of turpentine oil to anhydrous oxalic acid is 1:0.2-0.

7.

8. The use of the solid waste catalyst from an oil refinery in the preparation of borneol according to claim 6, characterized in that: The molar ratio of turpentine and anhydrous oxalic acid is 1:0.

5.

9. The use of the solid waste catalyst from an oil refinery in the preparation of borneol according to claim 6, characterized in that: The mass concentration of the sodium hydroxide solution in step (2) is 3% to 5%; the mass ratio of the esterification product to the sodium hydroxide solution in step (2) is 1:1 to 2.

10. The use of the solid waste catalyst from an oil refinery in the preparation of borneol according to claim 6, characterized in that: The saponification reaction in step (2) is carried out at 80° C. for 1 h.

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