A hydrogen peroxide working solution solvent system

Abstract

The application discloses a hydrogen peroxide working solution solvent system, which comprises the following components: aromatic hydrocarbon, imide derivative A and diisobutyl carbinol, wherein the aromatic hydrocarbon is 30-95 parts, preferably 60-85 parts, the imide derivative A is 2-30 parts, and the diisobutyl carbinol is 2-20 parts. The solvent system has good solubility for 2-alkyl anthraquinone, especially hydrogen anthraquinone, and the working solution has stable physical and chemical properties, low density and low viscosity. The hydrogen peroxide device operation efficiency can be greatly improved, high-quality and high-concentration hydrogen peroxide products can be directly produced, the safety and reliability of the production process can be improved, the asset investment and production operation cost can be reduced, and the solvent system has a good industrial application prospect.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of chemical synthesis, and particularly relates to a working liquid solvent system in a process for producing hydrogen peroxide by an anthraquinone method. BACKGROUND

[0002] At present, more than 99% of hydrogen peroxide products in the world are produced by the anthraquinone method process. The process uses 2-alkyl anthraquinone as a working liquid carrier, and performs catalytic hydrogenation and auto-oxidation on the anthraquinone working liquid in circulation and alternation, and then obtains hydrogen peroxide products of different concentrations after extraction, refining and concentration. The working liquid, as the "blood" of the anthraquinone method process, has a decisive influence on the production efficiency of each production unit. On the premise that the physicochemical properties of the working liquid completely meet the industrial requirements, the industry generally takes the mass of H2O2 generated by per unit volume of working liquid (i.e. the number of grams of H2O2 that can be produced per liter of working liquid) as an important index for evaluating production capacity.

[0003] Due to the large difference in molecular polarity of anthraquinone and its hydrogenation products, a single solvent is difficult to fully meet the above requirements of the working liquid, and the working liquid solvent system is generally composed of non-polar anthraquinone solvent and polar hydrogen anthraquinone solvent. At present, the working liquid solvent system has low solubility of anthraquinone and hydrogen anthraquinone, which leads to low anthraquinone conversion rate and low hydrogenation efficiency, further leading to large working liquid circulation amount in the device and small operation flexibility; the working liquid has large density and viscosity, which leads to poor extraction separation effect, seriously limits the product quality of hydrogen peroxide, leads to low product quality grade of hydrogen peroxide, high consumption of anthraquinone, and cannot meet the demand for high-purity hydrogen peroxide products.

[0004] CN1583546A discloses an aromatic hydrocarbon + trioctyl phosphate + tetrabutyl urea ternary solvent system. Compared with the traditional binary working liquid of aromatic hydrocarbon + trioctyl phosphate, the solubility of hydrogen anthraquinone is increased by about 10%, the hydrogenation efficiency of the working liquid is slightly improved, and the working liquid has suitable physicochemical indexes such as density and viscosity, but the system has high mutual solubility with water. CN1552618A discloses an aromatic hydrocarbon + trioctyl phosphate + methylcyclohexyl acetate ternary solvent system. Compared with the traditional binary working liquid of aromatic hydrocarbon + trioctyl phosphate, the solubility of 2-ethylanthraquinone in the system can be increased by 30 g / L, and the hydrogenation efficiency of the working liquid can be increased to 9-10 g / L, but the working liquid has large density and viscosity. EP0287421 discloses an aromatic hydrocarbon + N-phenyl N-ethyl benzamide (BEA) binary solvent system. Although the solubility of anthraquinone and hydrogen anthraquinone is obviously improved, the working liquid has high density and high water solubility, which leads to poor extraction separation effect, high residual carbon in hydrogen peroxide products, and poor application effect, and cannot meet the requirements of large-scale industrial application. SUMMARY

[0005] In view of the deficiencies of the prior art, the present application provides a hydrogen peroxide working liquid solvent system. The working liquid system has low density, viscosity and other physicochemical properties, has good solubility for anthraquinone and its hydrogen anthraquinone, can significantly improve the operation efficiency of the hydrogen peroxide device, reduce the asset investment and production operation cost, and has good industrial application prospect.

[0006] The hydrogen peroxide working liquid solvent system of the present application comprises the following components: aromatic hydrocarbon, imide derivative A and diisobutyl carbinol (DIBC); wherein the structural formula of the imide derivative A is: , wherein R1, R2 and R3 are each one of furan, aromatic hydrocarbon substituent, benzyl or alkane substituent with 1-8 carbon atoms, and the furan, aromatic hydrocarbon substituent, benzyl or alkane substituent further contains one or more functional groups of alkyl, alkoxy or ester group; the aromatic hydrocarbon is 30-95 parts by volume, preferably 60-80 parts, the diisobutyl carbinol is 2-20 parts, preferably 5-15 parts, and the imide derivative A is 5-30 parts, preferably 5-15 parts.

[0007] In the present application, the aromatic hydrocarbon is generally C9-C 10 The R1-R3 in the imide derivative A molecule is preferably C2-C6 normal / isoalkyl substituent group, and the carbon atom number of the substituent group at different positions can be allocated and adjusted according to the different physicochemical property requirements of the working liquid, but the total carbon atom number should not be higher than 20.

[0008] The present application also provides a hydrogen peroxide working liquid containing the above-mentioned solvent system, and the working carrier of the working liquid is one or more of anthraquinone and its derivatives, preferably 2-alkyl anthraquinone, and further preferably 2-ethyl anthraquinone, 2-butyl anthraquinone or 2-pentyl anthraquinone.

[0009] The present application also provides a hydrogenation process for producing hydrogen peroxide by the anthraquinone method, and the working liquid solvent system containing the imide derivative A and the aromatic hydrocarbon is used in the hydrogenation step. The process conditions of the hydrogenation step are as follows: hydrogenation temperature 30-80℃, pressure 0.1-0.7MPa, and the hydrogenation reactor can be in the form of fluidized bed, slurry bed or fixed bed.

[0010] The hydrogenation process can use the hydrogenation catalysts well known in the technical field of anthraquinone method, the hydrogenation active component is generally Pd, the carrier is generally alumina or silica gel, and an auxiliary component such as one or more of Mo, Na, K, Ni, Mg, Au, Ca, Fe and the like can also be added to the catalyst, the content of the hydrogenation active component is 0.05%-5% by weight of the hydrogenation catalyst component, and the content of the auxiliary component is 0.05%-3%.

[0011] The hydrogen peroxide working solution provided by the application can use air or pure oxygen or other conventional oxidants in the oxidation step in the anthraquinone process, and air is preferred. The process conditions of the oxidation step are generally as follows: the oxidation temperature is 25-70°C, and the pressure is 0.1-0.5 MPa.

[0012] Compared with the existing hydrogen peroxide working solution in the industry, the novel working solution provided by the application has the following characteristics: (1) good solubility for anthraquinone and hydrogenanthraquinone, the solubility of the working solution for 2-alkylanthraquinone can reach more than 180 g / L at normal temperature and pressure, and the solubility of the working solution for 2-alkylhydroanthraquinone can reach more than 99.8 g / L under the working conditions of the anthraquinone process, which can greatly increase the effective anthraquinone concentration in the working solution and improve the hydrogenation conversion rate of anthraquinone; (2) high hydrogenation efficiency, the hydrogenation efficiency of the working solution can reach more than 13 g / L under the conditions of the conventional anthraquinone hydrogenation catalyst in the industry; (3) the physicochemical properties of the working solution are suitable for the anthraquinone process, the mutual solubility of the working solution and water is low, the density and viscosity are small, and the working solution can meet the requirements of industrial production of hydrogen peroxide. DETAILED DESCRIPTION

[0013] The application will be further described below in combination with specific preferred embodiments, but the protection scope of the application is not limited in this way.

[0014] The application evaluates the solubility of different working solution systems for anthraquinone and hydrogenanthraquinone and the residual carbon index in the hydrogen peroxide product according to the following process:

[0015] (1) Anthraquinone solubility analysis: The solubility of anthraquinone is determined by using the "solid-liquid solubility equilibrium method". At 25°C, 2-alkylanthraquinone is gradually dissolved in 200 ml of working solution, and after the anthraquinone reaches the solid-liquid two-phase equilibrium and no longer dissolves, the working solution is left to stand for 2 hours, and after complete layering, 1 mL of the clear upper layer is dissolved in acetonitrile, diluted by 200 times, and then analyzed by high performance liquid chromatography to determine the anthraquinone concentration in the working solution. The high performance liquid chromatography test conditions are as follows: Agilent HPLC 1260, 4.6x250mmx5um Eclipse PAH reverse phase chromatographic column, mobile phase is acetonitrile / water=80 / 20, ultraviolet detector, detection wavelength is 255 nm, flow rate of mobile phase is 1 mL / min, injection volume is 1 mL, and chromatographic column temperature is 308.15 K. During the solubility determination process, the temperature accuracy is ±0.03°C, the high performance liquid analysis error is 0.1 mg, and the average value of three parallel experimental data is the experimental value of the measured anthraquinone solubility under the conditions.

[0016] (2) Hydroanthraquinone solubility analysis: The solubility of hydroanthraquinone is obtained by a critical hydrogenation experiment. The working solution is subjected to hydrogenation reaction in a transparent visual fixed bed reactor. The flow of the working solution in the fixed bed is observed by a laser detector. When the working solution reaches the critical crystallization precipitation state, the hydrogenation reaction is stopped. 1 mL of the hydrogenated solution is analyzed by high performance liquid chromatography. 5 mL of the hydrogenated solution is completely oxidized by air or oxygen. The mass concentration of hydrogen peroxide in the oxidized solution is analyzed by potassium permanganate (KMnO4) titration. Under the condition that there is no anthraquinone degradation product in the working solution, the solubility of hydroanthraquinone in different solvent systems is calculated by the hydrogenation efficiency value.

[0017] (3) Residual carbon analysis in hydrogen peroxide: The hydrogen peroxide in the oxidized solution is extracted with deionized water. After standing for more than 24 hours, the extraction phase and the raffinate phase are completely separated. 50 mL of the extraction solution is extracted at one time. The residual carbon content in the extraction solution is analyzed by a TOC residual carbon instrument.

[0018] The application also provides a synthesis method of the imide derivative A, comprising the following steps:

[0019] (1) The carboxylic acid A and the carboxylic acid B are dissolved in an organic solvent. Under the action of the catalyst A and the dehydrating agent A and under high temperature conditions, intermolecular dehydration reaction is carried out. After the reaction is completed, the dehydrating agent A is separated out. Then, extraction separation is carried out to obtain inorganic extraction liquid and organic raffinate liquid containing the anhydride C;

[0020] (2) Under the action of the catalyst B and the dehydrating agent B, the organic raffinate liquid containing the anhydride C obtained in step (1) is reacted with an ammonia source at low temperature for a period of time and then at high temperature for a period of time. After the reaction is completed, the inorganic phase is separated out to obtain an organic solution containing the imide D;

[0021] (3) A proper amount of halogenated hydrocarbon is added to the organic solution containing the imide D. Nucleophilic substitution reaction is carried out under weakly basic or strongly basic conditions. After the reaction is completed, washing and extraction are carried out to obtain an organic extraction phase. The solvent is removed by reduced pressure distillation. After drying, the imide derivative product is obtained.

[0022] In the method of the application, step (1) is to form a high molecular anhydride C with different structural functional groups through intermolecular dehydration of the carboxylic acid A and the carboxylic acid B containing different or same structural functional groups.

[0023] The dehydration reaction formula in step (1) is as follows:

[0024]

[0025] In the method of the present application, the carboxylic acid A (R1COOH) and the carboxylic acid B (R2COOH) in step (1) are substituted by furan, mono-substituted or poly-substituted aromatic hydrocarbon or benzyl, or straight-chain or branched alkane; and the substituents on the aromatic hydrocarbon or benzyl can be one or more of alkyl, alkoxy, ester, etc.

[0026] In the method of the present application, the organic solvent in step (1) is selected from one or more of xylene, mesitylene, chlorobenzene, N,N-dimethylformamide (DMF), ethyl acetate or pyridine; and the ratio of the amount of the organic solvent to the carboxylic acid is 2-10 mL / g, preferably 3-6 mL / g.

[0027] In the method of the present application, the catalyst A in step (1) is an aqueous solution of sodium methoxide and an iron salt, and the molar concentrations of the two are 0.01-5 mol / L and 0.1-10 mol / L, respectively; and the dehydrating agent A is P2O5.

[0028] In the method of the present application, the molar ratio of carboxylic acid A: carboxylic acid B: catalyst A: dehydrating agent A in step (1) is 1:1:0.15-0.5:0.5-5.

[0029] In the method of the present application, the dehydration reaction conditions in step (1) are as follows: normal pressure, 40-80℃, and reaction time is 18-25 hours. During the reaction, 300-400 mesh silica gel is used for layer-by-layer analysis (ethyl acetate: n-hexane = 2:1), and the target product is monitored by TCL. After the reaction, the reaction mixture is washed with deionized water for 3 times, then extracted with dichloromethane to obtain the organic phase, and the solvent is removed by reduced pressure distillation, and the target product is obtained as a white solid after drying in an oven.

[0030] In step (2) of the method of the present application, the reaction is first pre-hydrolyzed at a low temperature of 25-50℃, and then the ammoniaysis reaction is carried out at a high temperature of 210-230℃ after the reaction substrate is activated in the catalytic system.

[0031] The ammoniaysis reaction formula in step (2) is as follows:

[0032]

[0033] In the method of the present application, the catalyst B and the dehydrating agent B in step (2) are a mixed solution of triethylamine and potassium carbonate, and the molar concentrations of the two are 0.01-2 mol / L and 0.5-10 mol / L, respectively, and the molar ratio of triethylamine to potassium carbonate is 1:0.6-2.5.

[0034] In the method, the ammonia source in step (2) is ammonia, ammonia water, ammonium bicarbonate or urea, preferably ammonia or ammonia water, and the molar ratio of the ammonia source to the anhydride C is 1.2-10:1.

[0035] In the method, the pressure in step (2) is 0.1-0.5 MPa.

[0036] In the method, the low-temperature reaction condition in step (2) is 25-50 ℃ for 2-5 hours, and the high-temperature reaction condition is 210-230 ℃ for 1-1.5 hours.

[0037] In the method, the vacuum dehydration condition is preferably set during the high-temperature reaction in step (2), and the vacuum degree is -0.01 to -0.1 MPa.

[0038] In the method, the organic raffinate containing the anhydride C is preferably added to the mixed solution of the catalyst B and the dehydrating agent B (triethylamine and potassium carbonate) in a batch feeding or slow dripping manner in step (2), and the addition time is preferably 25-35 minutes.

[0039] In the method, the hydrogen halide generated by the nucleophilic substitution reaction (β-elimination reaction) in step (3) is dissolved in an alkaline aqueous solution, and the target main product is dissolved in an organic solvent.

[0040] The reaction equation of step (3) is as follows (taking bromoalkane as an example):

[0041]

[0042] In the method, the reaction condition in step (3) is 25-50 ℃ for 8-15 hours.

[0043] In the method, the drying condition in step (3) is 12-24 hours under the conditions of normal pressure and 120-140 ℃.

[0044] In the method, the washing in step (3) is generally 2-4 times using deionized water to wash the reaction mixture.

[0045] In the method, the halogenated alkane in step (3) is bromoalkane, chloroalkane or the like, preferably bromoalkane, and the molar ratio of the halogenated alkane to the carboxylic acid A is 1.2-1.5:1.

[0046] The application also provides a hydrogenation process for producing hydrogen peroxide by anthraquinone method, wherein the reaction process uses the working solution, the process conditions of the hydrogenation process are as follows: hydrogenation temperature is 30-80℃, pressure is 0.1-0.7MPa, and the hydrogenation reactor can be a fluidized bed, a slurry bed or a fixed bed. The hydrogenation process can use a hydrogenation catalyst known in the technical field of anthraquinone method, the hydrogenation active component is generally Pd, the carrier is generally alumina or silica gel, and an auxiliary component such as one or more of Mo, Na, K, Ni, Mg, Au, Ca, Fe and the like can also be added to the catalyst, the content of the hydrogenation active component is 0.05%-5% by weight of the hydrogenation catalyst component, and the content of the auxiliary component is 0.05%-3%.

[0047] In the application process of the working solution of hydrogen peroxide, the oxidation step can use air or pure oxygen or other conventional oxidants, and air is preferred. The process conditions of the oxidation step are generally as follows: oxidation temperature is 25-70℃, and pressure is 0.1-0.5MPa. DETAILED DESCRIPTION

[0049] Example 1

[0050] With the N-tert-butyl di-tert-butyl imide synthesis process as an example, the specific synthesis process of the imide derivative A is as follows: 176.2 g of tert-butyl acid, 75 g of P2O5, 50 mL of a mixed solution of sodium methoxide and iron salt (6.8 g of sodium methoxide and 10 g of ferrous nitrate), and the system temperature is raised to 65°C, and the reaction is carried out for 20 hours, and then the reaction is stopped, and the P2O5 powder is filtered out, and the reaction liquid is transferred to a Buchner funnel and washed with deionized water for three times, and the inorganic aqueous solution is separated; the organic residual liquid is returned to the reaction kettle, the mixed gas of ammonia and nitrogen is filled into the reaction system, the pressure is increased to 0.25-0.3 MPa, and the reaction is carried out at 35°C for 2 hours, and 50 mL of a mixed solution of 45-50 wt.% potassium carbonate and triethylamine is pumped into the reaction system during the reaction, the pumping time is 20 min, and then the system temperature is increased to 120°C and the reaction is carried out for 1.5 hours, and then the inorganic phase in the mixed liquid is separated after the system is cooled to room temperature; 165 g of 1-bromobutane is added to the remaining organic phase reaction liquid, and the reaction is carried out at 35°C for 12 hours, and then the reaction system is monitored by TCL, and the composition of the raw materials and the product is analyzed by using 300-400 mesh silica gel, and then the reaction product is washed with deionized water for three times, and the reaction liquid is vacuum dehydrated under the condition of-0.6 to-0.75 MPa vacuum degree, and then the product is washed with dichloromethane, and the solvent is distilled under reduced pressure, and then the product is placed in an oven and dried for 4 hours, and finally the N-n-butyl di-tert-butyl imide white crystal is obtained. The obtained product is analyzed by 1H NMR and MS spectrum, and it is confirmed that the product is N-n-butyl di-tert-butyl imide, and the total yield is 95.6%.

[0051] 1H NMR (500 MHz, CDCl3) δ = 0.9-1.0 (m, 18H), 1.9-2.05 (m, 1H), 2.05-2.15 (m, 2H), 2.25-2.4 (m, 4H), 3.4-3.45 (s, 2H);

[0052] MS [M+H] + : 241.7.

[0053] Example 2

[0054] The synthesis process of N-isopentyl 1-isopropyl-2-tert-butyl imide was taken as an example, and the preparation method was similar to that of Example 1, except that the raw materials and the amount of carboxylic acids A, B and halogenated alkanes were slightly adjusted according to the target product. 88.1 g of tert-butyl acid, 74.5 g of propionic acid, 71 g of P2O5, 30 mL of sodium methoxide and a mixture of iron salts (5.4 g of sodium methoxide and 9.1 g of ferrous nitrate) were added into a 500 mL reaction kettle at one time. After the intermediate product was prepared according to the preparation method in Example 1, 165 g of 1-bromopentane was added to the reaction solution of the intermediate product, and the reaction was carried out at 35°C for 12 hours. The silica gel with a particle size of 300~400 μm was selected by using the layer-by-layer analysis method (ethyl acetate: n-hexane = 2:1), and the composition of the raw materials and the product in the reaction system was monitored by TCL. After the reaction was completed, the reaction product was washed with deionized water for 3 times, and then washed with dichloromethane. The solvent was distilled under reduced pressure, and the product was dried in an oven for 4 hours. Finally, the white crystal product was obtained. The obtained product was confirmed to be N-isopentyl 1-isopropyl-2-tert-butyl imide structure by 1H NMR and MS spectrum analysis, and the yield was 95.6% (calculated based on the raw material carboxylic acid).

[0055] 1H NMR (500 MHz, CDCl3) δ = 0.95~1.10 (m, 18H), 2.07~2.17 (m, 1H), 2.25~2.4 (m, 2H), 2.5~2.55 (m, 2H), 3.45~3.55 (s, 2H);

[0056] MS [M+H] + : 241.3.

[0057] Example 3

[0058] The mixture of C9~C 10 aromatic hydrocarbon / diisobutyl carbinol / N-tert-butyl di-tert-butyl imide = 75 / 5 / 20 was used as the solvent system to prepare the 2-ethylanthraquinone working solution.

[0059] The viscosity of the working solution was analyzed according to GB 11137-20, and the hydrogenation reaction evaluation of the above working solution was carried out in a 500 ml intermittent stirring reaction kettle. The hydrogenation temperature was 45~50°C, the hydrogenation pressure was 0.1~0.3 MPa, and the stirring rate was 300~400 rpm. The obtained hydrogenated liquid was oxidized with air at normal pressure and 30~50°C for 15~30 min. After the oxidation liquid was extracted with pure water for 4 times, the hydrogen peroxide content in the extracted liquid was determined by potassium permanganate titration method, and the hydrogenation efficiency of the working solution was calculated. The catalyst used in the hydrogenation experiment was the Pd / Al2O3 catalyst commonly used in the hydrogen peroxide industry, with a particle size of 0.4~0.5 mm and a pore volume of 0.6~0.7 cm 3 / g, specific surface area 150-180 m2 / g, Pd content 0.25-0.30 wt%.

[0060] The test results show that the density of the working liquid solvent system is 0.917 g / cm 3 , the viscosity is 2.331 Pa·s, the solubility of 2-ethylanthraquinone in the working liquid solvent system is 195.1 g / L at 25℃ under normal pressure, the solubility of 2-ethylhydroanthraquinone is 101.8 g / L at 50-55℃ under 0.2-0.3 MPa, the hydrogenation efficiency of the working liquid with 2-ethylanthraquinone mass concentration of 180 g / L is 13.6 g / L, and the organic residual carbon in the hydrogen peroxide product is 150-160 ppm.

[0061] Example 4

[0062] A mixture of C9-C 10 aromatic hydrocarbon / diisobutyl carbinol / N-isoamyl 1-isopropyl-2-tert-butyl imide = 70 / 15 / 15 is used as the solvent system to prepare a 2-ethylanthraquinone working liquid; the working liquid system is evaluated for performance under conditions similar to those of Example 3, except that the hydrogenation temperature is 30-40℃. The test results show that the density of the working liquid solvent system is 0.919 g / cm 3 , the viscosity is 2.261 Pa·s, the solubility of 2-ethylanthraquinone in the working liquid system is 192.2 g / L at 25℃ under normal pressure, the solubility of 2-ethylhydroanthraquinone is 99.8 g / L at 30-40℃ under 0.2-0.3 MPa, the hydrogenation efficiency of the working liquid with 2-ethylanthraquinone mass concentration of 180 g / L is 13.1 g / L, and the organic residual carbon in the hydrogen peroxide product is 140-155 ppm.

[0063] Example 5

[0064] A mixture of C9-C 10 aromatic hydrocarbon / diisobutyl carbinol / N-isoamyl 1-isopropyl-2-tert-butyl imide = 70 / 15 / 15 is used as the solvent system to prepare a 2-ethylanthraquinone working liquid; the working liquid system is evaluated for performance under conditions similar to those of Example 3, except that the hydrogenation temperature is 30-40℃. The test results show that the density of the working liquid solvent system is 0.919 g / cm 3, the viscosity is 2.343 Pa s, the solubility of 2-pentylanthraquinone in the working solution system is 477.3 g / L at 25℃ under normal pressure, the solubility of 2-pentylhydroanthraquinone is 138.1-145.8 g / L under the conditions of 55-65℃ and 0.25-0.40 MPa, the hydrogenation efficiency of the working solution with 2-pentylanthraquinone mass concentration of 460 g / L is 15.1-15.5 g / L, and the organic residual carbon in the hydrogen peroxide product is 150-160 ppm.

[0065] Comparative Example 1

[0066] According to CN1552618A, Example 3, a working solution was prepared, and the performance of the working solution system was analyzed under the conditions of Example 1. 10 The aromatic hydrocarbon / phosphoric acid trioctyl ester = 75 / 25 mixture was used as a solvent system to prepare a 2-ethylanthraquinone working solution, and the performance of the working solution system was analyzed under the conditions of Example 1. The test results showed that the density of the working solution was 0.927 g / cm 3 , the viscosity was 2.355 Pa s, the solubility of 2-ethylanthraquinone in the C9-C 10 aromatic hydrocarbon / phosphoric acid trioctyl ester working solution system was 123-130 g / L, the solubility of 2-ethylhydroanthraquinone was 68.5-70 g / L under the conditions of 53-60℃ and 0.25-0.30 MPa, the hydrogenation efficiency of the working solution with 2-ethylanthraquinone mass concentration of 125 g / L was 6.5-7.3 g / L, and the organic residual carbon in the hydrogen peroxide product was 205 ppm.

[0067] Comparative Example 2

[0068] According to CN1552618A, Example 3, a working solution was prepared, and the performance of the working solution system was analyzed under the conditions of Example 1.

[0069] The test results showed that the density of the working solution was 0.943 g / cm 3 , the viscosity was 2.511 Pa s, the solubility of 2-ethylanthraquinone in the C9-C

[0070] Comparative Example 3

[0071] According to EP0287421, an aromatic hydrocarbon+N-phenyl N-ethyl benzamide (BEA) binary solvent system was used to prepare a 2-ethylanthraquinone working solution, and the performance of the working solution system was analyzed under the conditions of Example 1. The test results showed that the density of the working solution solvent system was 0.929 g / cm 3The viscosity is 2.432 Pa s, the solubility of 2-ethylanthraquinone in the working solution system is 155-163 g / L under the condition of 25 DEG C and normal pressure, the solubility of 2-ethylanthrahydroquinone is 85-89 g / L under the condition of 55-60 DEG C and 0.25-0.30 MPa, the hydrogenation efficiency of the working solution with the mass concentration of 2-ethylanthraquinone being 150 g / L is 10.33 g / L, and the organic residual carbon in the hydrogen peroxide product is 554.8 ppm.

Claims

1. A hydrogen peroxide working solution solvent system, characterized in that... It includes the following components: aromatic hydrocarbon, imide derivative A, and diisobutylmethanol; wherein the structural formula of imide derivative A is: R1, R2, and R3 are one of the following: furan, aromatic, benzyl, or alkane substituents with 1 to 8 carbon atoms; by volume, aromatics are 30 to 95 parts, diisobutylmethanol is 2 to 20 parts, and imide derivative A is 5 to 30 parts.

2. The hydrogen peroxide working solution solvent system according to claim 1, characterized in that, By volume, the aromatic hydrocarbons are 60-80 parts, the diisobutylmethanol is 5-15 parts, and the imide derivative A is 5-15 parts.

3. The hydrogen peroxide working solution solvent system according to claim 1, characterized in that: The furan, aromatic, benzyl, or alkane substituents further contain one or more functional groups selected from alkyl, alkoxy, and ester groups.

4. The hydrogen peroxide working solution solvent system according to claim 1, characterized in that: The aromatic hydrocarbons mentioned are C9~C 10 Aromatic hydrocarbons; in the imide derivative A molecule, R1~R3 ​​are one of the normal / isomeric alkyl substituents of C2~C6.

5. The hydrogen peroxide working solution solvent system according to any one of claims 1 to 4, characterized in that, The method for synthesizing the imide derivative A includes the following steps: (1) Dissolving carboxylic acid A and carboxylic acid B in an organic solvent, and carrying out an intermolecular dehydration reaction under the conditions of catalyst A, dehydrating agent A and high temperature. After the reaction, dehydrating agent A is separated, and then extraction is performed to obtain an inorganic extract and an organic raffinate containing acid anhydride C; (2) Under the action of catalyst B and dehydrating agent B, the organic raffinate containing acid anhydride C obtained in step (1) is reacted with an ammonia source at low temperature for a period of time, and then at high temperature for a period of time. After the reaction, the inorganic phase is separated to obtain an organic solution containing imide D; (3) Adding an appropriate amount of haloalkanes to the organic solution containing imide D, and carrying out a nucleophilic substitution reaction under weak or strong alkaline conditions. After the reaction, washing and extraction are performed to obtain an organic extract phase, the solvent is removed by vacuum distillation, and the product is dried to obtain the imide derivative.

6. The hydrogen peroxide working solution solvent system according to claim 5, characterized in that: The method for synthesizing imide derivative A is characterized in that: the carboxylic acid A in step (1) is R1COOH and the carboxylic acid B is R2COOH, wherein R1 and R2 are respectively one of furan, monosubstituted or polysubstituted aromatic hydrocarbon substituent or benzyl, or straight-chain or branched alkane substituent; wherein the substituent on the aromatic hydrocarbon substituent or benzyl is one or more of alkyl, alkoxy, and ester groups.

7. The hydrogen peroxide working solution solvent system according to claim 5, characterized in that: In the method for synthesizing imide derivative A, the organic solvent in step (1) is selected from one or more of xylene, trimethylbenzene, chlorobenzene, N,N-dimethylformamide, ethyl acetate or pyridine; the ratio of organic solvent to carboxylic acid is 2~10 mL / g.

8. The hydrogen peroxide working solution solvent system according to claim 5, characterized in that: In the synthesis method of imide derivative A, the catalyst A in step (1) is an aqueous solution of sodium methoxide and iron salt, with molar concentrations of 0.01~5 mol / L and 0.1~10 mol / L, respectively, and the dehydrating agent A is P2O5.

9. The hydrogen peroxide working solution solvent system according to claim 5, characterized in that: In the synthesis method of imide derivative A, the molar ratio of carboxylic acid A: carboxylic acid B: catalyst A: dehydrating agent A in step (1) is 1: 1: 0.15~0.5: 0.5~5.

10. The hydrogen peroxide working solution solvent system according to claim 5, characterized in that: In the synthesis method of imide derivative A, the dehydration reaction conditions in step (1) are: atmospheric pressure, 40~80℃ for 18~25 hours.

11. The hydrogen peroxide working solution solvent system according to claim 5, characterized in that: In the synthesis method of imide derivative A, the catalyst B and dehydrating agent B mentioned in step (2) are a mixed solution of triethylamine and potassium carbonate, with molar concentrations of 0.01~2 mol / L and 0.5~10 mol / L, respectively, and the molar ratio of triethylamine to potassium carbonate is 1:0.6~2.

5.

12. The hydrogen peroxide working solution solvent system according to claim 5, characterized in that: In the synthesis method of imide derivative A, the ammonia source in step (2) is ammonia gas, ammonia water, ammonium bicarbonate or urea, and the molar ratio of ammonia source to acid anhydride C is 1.2~10:

1.

13. The hydrogen peroxide working solution solvent system according to claim 5, characterized in that: In the synthesis method of imide derivative A, the low-temperature reaction conditions are: reaction at 25~50℃ for 2~5 hours; the high-temperature reaction conditions are: reaction at 210~230℃ for 1~1.5 hours.

14. The hydrogen peroxide working solution solvent system according to claim 5, characterized in that: In the synthesis method of imide derivative A, the reaction conditions in step (3) are: reaction at 25~50℃ for 8~15 hours; the haloalkane is a bromoalkane or a chloroalkane, and the molar ratio of haloalkane to carboxylic acid A is 1.2~1.5:

1.

15. The hydrogen peroxide working solution solvent system according to claim 14, characterized in that, The haloalkanes mentioned are bromoalkanes.

16. A hydrogen peroxide working solution, characterized in that: The invention includes the hydrogen peroxide working solvent system and working carrier as described in any one of claims 1 to 15, wherein the working carrier is one or more of anthraquinone and its derivatives.

17. The hydrogen peroxide working solution according to claim 16, characterized in that: The working carrier is 2-alkylanthraquinone.

18. A hydrogenation process for producing hydrogen peroxide using the anthraquinone method, characterized in that: The hydrogenation step uses the hydrogen peroxide working solution solvent system as described in any one of claims 1 to 15; the process conditions for the hydrogenation step are: hydrogenation temperature 25 to 80°C, pressure 0.1 to 0.7 MPa.

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