Working solution solvent system for hydrogen peroxide production by anthraquinone process

Abstract

The application discloses a solvent system of working solution for hydrogen peroxide production by an anthraquinone method, which comprises the following components: aromatic hydrocarbon, imide derivative A and tri-octyl phosphate (TOP); the aromatic hydrocarbon is 30-95 parts, preferably 60-80 parts, the tri-octyl phosphate is 2-30 parts, and the imide derivative A is 2-30 parts in volume fraction. The working solution solvent system has good dissolving and mass transfer capacity for hydrogen, anthraquinone and hydrogen anthraquinone, the hydrogenation efficiency can reach more than 13 g / L, the mutual solubility of the working solution and water is low, the physical and chemical properties are stable, the working solution meets the use requirements of the anthraquinone method hydrogen peroxide production process, the production efficiency of the anthraquinone method hydrogen peroxide production process can be obviously improved, and the working solution 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] In recent years, green production processes such as direct oxidation of propylene / hydrogen peroxide to prepare propylene oxide and oxidation of cyclohexanone via ammoximation to prepare caprolactam are increasingly mature in China, environmental protection requirements are increasingly stringent, and hydrogen peroxide (H2O2) as a clean and environmentally friendly chemical product is widely used in chemical synthesis, environmental protection, paper bleaching, textile printing and dyeing, medical disinfection, electronics and other fields, and the market demand is increasing year by year.

[0003] At present, more than 99% of hydrogen peroxide products in the world are produced by the anthraquinone process. The process uses 2-alkyl anthraquinone as a working carrier, and the anthraquinone working solution is cyclically and alternately subjected to catalytic hydrogenation and auto-oxidation reaction, and then extracted, refined and concentrated to obtain hydrogen peroxide products of different concentrations. As the "blood" of the anthraquinone process, the working solution has a decisive influence on the production efficiency of each production unit. Generally, the production capacity of the working solution is evaluated by the mass of H2O2 generated per unit volume of working solution (i.e. the number of grams of H2O2 that can be produced per liter of working solution).

[0004] However, since the large-scale industrialization of the anthraquinone hydrogen peroxide production process in the late 20th century, the solvent system of the hydrogen peroxide working solution still has the following main technical problems: (1) the solubility of anthraquinone and hydroanthraquinone in the working solution is low, which leads to low conversion rate of anthraquinone reaction, large amount of working solution circulation, and small operation flexibility of the device; (2) the anthraquinone hydrogen peroxide production process is a typical gas-liquid-solid three-phase reaction process, and the existing working solution has low hydrogen solubility and mass transfer capacity, which leads to low hydrogen content in the working solution, further leads to slow anthraquinone hydrogenation reaction rate, poor selectivity of catalytic hydrogenation, high degradation rate of anthraquinone, large consumption of anthraquinone, and serious restriction on the production efficiency of the device; (3) the hydrogenation efficiency of the working solution is low, which leads to low quality grade of the hydrogen peroxide product and cannot meet the demand for high-purity hydrogen peroxide products.

[0005] CN1552618A discloses an aromatic hydrocarbon + trioctyl phosphate + methylcyclohexyl acetate ternary solvent system, compared with the traditional aromatic hydrocarbon + trioctyl phosphate binary working solution, the solubility of 2-ethylanthraquinone can be increased by 30 g / L, and the hydrogenation efficiency of the working solution can be increased to 9~9.5 g / L, but the density and viscosity of the working solution are relatively large, the hydrogen mass transfer capacity is relatively low, and the anthraquinone hydrogenation conversion rate under working conditions is nearly 40%. EP0287421 discloses an aromatic hydrocarbon + N-phenyl N-ethyl benzamide (BEA) binary solvent system, although the solubility of hydrogen, anthraquinone and hydrogenanthraquinone of the system is obviously improved, the density of the working solution is relatively high, and the water solubility is large, which leads to poor extraction separation effect, high residual carbon in hydrogen peroxide product, and poor application effect, which cannot meet the requirements of industrial application. CN111071993A discloses an aromatic hydrocarbon + tetraalkyl bisamide derivative binary solvent system, which can significantly improve the solubility and mass transfer of the working solution to hydrogen, and the solubility of 2-ethylanthraquinone can be increased to more than 180 g / L, and the hydrogenation efficiency can be increased to more than 13 g / L, which can meet the requirements of industrial application. However, the synthesis process of tetraalkyl bisamide derivative molecules is complex, and the production cost is high, which affects the industrial application of the working solution system. SUMMARY

[0006] In view of the shortcomings of the prior art, the present application provides an anthraquinone method for producing hydrogen peroxide working solution solvent system. The working solution has good solubility and mass transfer capacity for hydrogen, anthraquinone and hydrogenanthraquinone, the hydrogenation efficiency is more than 13 g / L, the mutual solubility of the working solution and water is low, and the physical and chemical properties are stable, which can meet the use requirements of the anthraquinone method for producing hydrogen peroxide, can improve the production efficiency of the anthraquinone method for producing hydrogen peroxide, and has good industrial application prospect.

[0007] The anthraquinone method for producing hydrogen peroxide working solution solvent system of the present application comprises the following components: aromatic hydrocarbon, imide derivative A and trioctyl phosphate (TOP); wherein the structure of the imide derivative A is: , wherein R1, R2 and R3 are one of furan, aromatic hydrocarbon substituent, benzyl or alkane substituent with 1~8 carbon atoms; the furan, aromatic hydrocarbon substituent, benzyl or alkane substituent also contains one or more functional groups of alkyl, alkoxy, ester group; the aromatic hydrocarbon is 30~95 parts, preferably 60~80 parts, the trioctyl phosphate is 2~30 parts, preferably 5~15 parts, and the imide derivative A is 2~30 parts, preferably 5~15 parts, in volume fraction.

[0008] In the present application, the aromatic hydrocarbon is generally C9~C 10 The aromatic hydrocarbon; R1~R3 in the imide derivative A molecule are preferably C2~C6 normal / isomer alkyl substituent groups, the carbon atom number of the substituent groups at different positions can be allocated and adjusted according to the different physical and chemical property requirements of the working solution, but the total carbon atom number is generally not higher than 20.

[0009] The present application also provides a working solution for hydrogen peroxide production by anthraquinone process, which comprises a working solution solvent system and a working carrier, the working solution solvent system comprises imide derivative A, aromatic hydrocarbon and phosphoric acid trioctyl ester, and the working carrier is one or more of anthraquinone and its derivatives, preferably 2-alkyl anthraquinone, and further preferably 2-ethyl anthraquinone or 2-butyl anthraquinone or 2-pentyl anthraquinone.

[0010] The present application also provides a hydrogenation process for hydrogen peroxide production by anthraquinone process, wherein the hydrogenation step adopts a working solution solvent system comprising imide derivative A and aromatic hydrocarbon, and the process conditions for the hydrogenation step are as follows: hydrogenation temperature is 30-80℃, pressure is 0.1-0.7MPa, and the hydrogenation reactor can be in the form of fluidized bed, slurry bed or fixed bed.

[0011] The hydrogenation process can adopt a hydrogenation catalyst known in the technical field of anthraquinone process, 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% based on the weight of the hydrogenation catalyst component, and the content of the auxiliary component is 0.05%-3%.

[0012] In the application of the working solution for hydrogen peroxide to the anthraquinone process, the oxidation step can adopt air or pure oxygen or other conventional oxidants, and air is preferred. The process conditions for the oxidation step are generally as follows: oxidation temperature is 25-70℃, and pressure is 0.1-0.5MPa.

[0013] The synthesis method of the imide derivative A of the present application comprises the following steps:

[0014] (1) Carboxylic acid A and carboxylic acid B are dissolved in an organic solvent, and intermolecular dehydration reaction is carried out under the action of catalyst A, dehydrating agent A and high temperature, after the reaction is completed, the dehydrating agent A is separated out, and then extraction separation is carried out to obtain inorganic extraction liquid and organic raffinate containing acid anhydride C;

[0015] (2) The organic raffinate containing acid anhydride C obtained in step (1) is reacted with an ammonia source under the action of catalyst B and dehydrating agent B, first 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 imide D;

[0016] (3) An appropriate amount of halogenated hydrocarbon is added to the organic solution containing imide D, and 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, and drying is carried out to obtain the imide derivative product.

[0017] In the method of the present application, step (1) is to form a high molecular anhydride C with different structural functional groups by intermolecular dehydration of carboxylic acid A and carboxylic acid B with different or same structural functional groups.

[0018] The intermolecular dehydration reaction formula of step (1) is as follows:

[0019]

[0020] In the method of the present application, the carboxylic acid A (R1COOH) and carboxylic acid B (R2COOH) of 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.

[0021] In the method of the present application, the organic solvent of step (1) is selected from one or more of xylene, mesitylene, chlorobenzene, N,N-dimethylformamide (DMF), ethyl acetate or pyridine, etc.; and the ratio of the amount of the organic solvent to the carboxylic acid is 2-10 mL / g, preferably 3-6 mL / g.

[0022] In the method of the present application, the catalyst A of step (1) is an aqueous solution of sodium methoxide and 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.

[0023] In the method of the present application, the molar ratio of carboxylic acid A: carboxylic acid B: catalyst A: dehydrating agent A of step (1) is 1:1:0.15-0.5:0.5-5.

[0024] In the method of the present application, the dehydration reaction conditions of step (1) are as follows: normal pressure, 40-80℃, reaction for 18-25 hours. During the reaction, 300-400 mesh silica gel is used by layer-by-layer analysis method (ethyl acetate: n-hexane = 2:1), and the target product is tracked and monitored by TCL. After the reaction is completed, the reaction mixture is washed with deionized water for 3 times, then extracted with dichloromethane to obtain organic extract phase, and the solvent is removed by reduced pressure distillation and dried in an oven to obtain the target product white solid.

[0025] In the method of the present application, step (2) is first pre-hydrolyzed at a low temperature of 25-50℃, and then subjected to ammonolysis reaction at a high temperature of 210-230℃ after the reaction substrate is activated in the catalytic system.

[0026] The ammonolysis reaction formula of step (2) is as follows:

[0027]

[0028] In the method, the catalyst B and the dehydrating agent B in step (2) are a mixed solution of triethylamine and potassium carbonate, 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.

[0029] 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.

[0030] In the method, the pressure in step (2) is 0.1-0.5 MPa.

[0031] In the method, the low-temperature reaction condition in step (2) is 25-50°C for 2-5 hours, and the high-temperature reaction condition is 210-230°C for 1-1.5 hours.

[0032] 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.

[0033] In the method, the organic raffinate containing the anhydride C is preferably added in batches or slowly dripped into the mixed solution of the catalyst B and the dehydrating agent B (triethylamine and potassium carbonate) in step (2), and the addition time is preferably 25-35 minutes.

[0034] In step (3), the hydrogen halide generated by the nucleophilic substitution reaction (β-elimination reaction) is dissolved in an alkaline aqueous solution, and the target main product is dissolved in an organic solvent.

[0035] The reaction equation of step (3) is as follows (taking bromoalkane as an example):

[0036]

[0037] In the method, the reaction condition in step (3) is 25-50°C for 8-15 hours.

[0038] In the method, the drying condition in step (3) is 12-24 hours under the conditions of normal pressure and 120-140°C.

[0039] In the method, the washing in step (3) is generally 2-4 times with deionized water.

[0040] In the method, the halogenated alkane in step (3) is bromoalkane, chloroalkane, etc., preferably bromoalkane, and the molar ratio of the halogenated alkane to the carboxylic acid A is 1.2-1.5:1.

[0041] Compared with the existing hydrogen peroxide working solution in industry, the new 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 under normal temperature and pressure, and the solubility of the working solution for 2-alkylhydroanthraquinone can reach more than 100 g / L under anthraquinone working conditions, which can greatly increase the effective anthraquinone concentration in the working solution and improve the hydrogenation conversion rate of anthraquinone; (2) high hydrogenation efficiency and low anthraquinone degradation rate, the hydrogenation efficiency of the working solution can reach more than 13 g / L under the condition of industrial conventional anthraquinone hydrogenation catalyst; (3) good hydrogen solubility and mass transfer, and inhibiting the degradation rate of anthraquinone in the working solution; (4) the physicochemical properties of the working solution are suitable for anthraquinone process, and can meet the requirements of industrial production of hydrogen peroxide. DETAILED DESCRIPTION

[0042] The application will be further described below in combination with specific preferred embodiments, but the protection scope of the application is not limited thereby.

[0043] The application evaluates the solubility of different working solution systems for anthraquinone and hydrogenanthraquinone and the residual carbon index in hydrogen peroxide products according to the following process:

[0044] (1) Anthraquinone solubility analysis: The solubility of anthraquinone is determined by using the "solid-liquid solubility equilibrium method". Under the condition of constant temperature of 25℃, 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, 4.6×250mm×5um 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 amount is 1 ml, and chromatographic column temperature is 35℃. During the solubility determination process, the temperature accuracy is ±0.03℃, the high performance liquid analysis error is 0.1 mg, and the average value of three parallel experiment data is the experimental value of the measured anthraquinone solubility under the condition.

[0045] (2) Solubility analysis of hydrogenanthraquinone: The solubility of hydrogenanthraquinone is obtained from the 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 hydrogenated solution is taken for high performance liquid chromatography analysis of the composition of the hydrogenated solution. Meanwhile, 5 mL of hydrogenated solution is completely oxidized by air or oxygen. The mass concentration of hydrogen peroxide in the oxidized solution is analyzed by potassium permanganate (KMn04) titration method. Under the condition that there is no anthraquinone degradation product in the working solution, the solubility of hydrogenanthraquinone in different solvent systems is calculated by hydrogenation efficiency value.

[0046] (3) Dissolution and mass transfer analysis of hydrogen: The gas-liquid phase equilibrium data of the working solution solvent system and hydrogen are determined and analyzed by using the "dissolution saturation method". The analysis device mainly consists of a 500 ml stainless steel mechanical stirred tank, a vacuum pumping system and a pressure and temperature control system. Before measurement, 300 ml of the solvent to be measured is placed in the reactor for vacuum degassing. The measurement system is tested for air tightness by N2. If there is no pressure change in the system within 1 hour, it indicates that the air tightness of the measurement system is good. The working solution to be measured is heated to the predetermined temperature. After N2 in the device is replaced three times by rapidly introducing H2, the stirring in the tank is started and the change of the hydrogen partial pressure in the system with the measurement time is recorded. The solubility and mass transfer coefficient of hydrogen in different solvent systems are calculated by the following formula: k a) The calculation process is as follows:

[0047] The dissolution and absorption of H2 by the working solution liquid phase main body in the constant volume closed reactor result in that the hydrogen partial pressure in the reactor is a function of the physical dissolution time. The pressure gradually decreases with the contact time, and the change relationship is shown in formula 1:

[0048] (Formula 1)

[0049] Among them, N L is the mass transfer rate of H2 in the solvent system, R is the gas constant, P and T are the corresponding pressure and temperature under the test conditions, V G is the gas phase volume in the test system. Integrating formula 1 gives: (Formula 2)

[0050] The mass balance equation of H2 in the working solution above and the Henry equation are related to obtain: (Formula 3)

[0051] Let α , and the initial state P = P0, t = 0, mass transfer P = P i , t = t as the boundary condition, formula 3 is integrated to obtain formula 4 The volume transfer coefficient of H2 in the working liquid-liquid phase body is calculated.

[0052] Example 1

[0053] The synthesis process of N-tert-butyl di-tert-butyl imide is taken as an example, and the specific synthesis process of imide derivative A is as follows: 176.2 g of tert-butyl acid, 75 g of P2O5, 50 mL of mixed solution of sodium methoxide and iron salt (6.8 g of sodium methoxide and 10 g of ferrous nitrate) are put into a 500 mL reaction kettle at one time, the temperature of the system is raised to 65°C, and the reaction is carried out for 20 hours after constant temperature reaction, then P2O5 powder is filtered out, 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; during the reaction, 50 mL of mixed solution of 45-50 wt% potassium carbonate and triethylamine is pumped into the reaction system, the pumping time is 20 min, then the temperature of the system is increased to 220°C, and the reaction is carried out for 1.5 hours; after the system is cooled to room temperature, the inorganic phase in the mixed solution is separated; 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; the silica gel with a particle size of 300-400 μm is selected by using the stepwise analysis method (ethyl acetate:n-hexane=2:1), the composition of the raw material and the product in the reaction system is monitored by TCL, after the reaction is completed, the reaction product is washed with deionized water for three times, and the reaction liquid is vacuum dehydrated under the condition of vacuum degree of-0.6 to-0.75 MPa; the product is washed with dichloromethane, the solvent is distilled under reduced pressure, and the product is dried in an oven for 4 hours; finally, 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%.

[0054] 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);

[0055] MS [M+H] + : 241.7.

[0056] Example 2

[0057] 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 in 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 a mixed solution of sodium methoxide and iron salt (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 obtained by 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 265℃ for 12 hours. The silica gel with a particle size of 300~400 μm was selected by using the step-by-step 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).

[0058] 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);

[0059] MS [M+H] + : 241.3.

[0060] Example 3

[0061] The mixture of C9~C 10 aromatic hydrocarbon / trioctyl phosphate / N-tert-butyl di-tert-butyl imide = 75 / 15 / 10 was used as the solvent system to prepare the 2-ethylanthraquinone working solution.

[0062] The above working solution was evaluated by hydrogenation reaction in a 500 ml intermittent stirring reaction kettle. The hydrogenation temperature was 45~50℃, the hydrogenation pressure was 0.1~0.3 MPa, and the stirring rate was 300~400 rpm. The obtained hydrogenation liquid was oxidized with air at normal pressure and 30~50℃ for 15~30 min. The hydrogen peroxide content in the extracted liquid was determined by potassium permanganate titration method after the oxidation liquid was extracted with pure water for 4 times. 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, a pore volume of 0.6~0.7 cm 3 / g, a specific surface area of 150~180 m 2 / g, and a Pd content of 0.25~0.30 wt%.

[0063] The test results show that the solubility of 2-ethylanthraquinone in the working solution solvent system is 183.5 g / L at 25℃, the solubility of 2-ethylhydroanthraquinone is 97.8 g / L at 50-55℃ and 0.25-0.28 MPa, the hydrogenation efficiency of the working solution with a 2-ethylanthraquinone mass concentration of 180 g / L is 13.2 g / L, the solubility of H2 in the working solution system is 1.45 mmol / L, and the mass transfer factor of H2 is 0.162 s -1 .

[0064] Example 4

[0065] A mixture of C9-C 10 aromatic hydrocarbon / phosphoric acid trioctyl ester / N-ethyl 1-alkoxy-2-heptyl imide = 60 / 20 / 20 by volume fraction is used as the solvent system, and a 2-ethylanthraquinone working solution is prepared; the working solution system is subjected to performance evaluation under the process conditions of Example 3. The test results show that the solubility of 2-pentylanthraquinone in the working solution system is 432.1 g / L at 25℃ and normal pressure, the solubility of 2-pentylhydroanthraquinone is 145.2 g / L at 60-70℃ and 0.25-0.30 MPa, the hydrogenation efficiency of the working solution with a 2-pentylanthraquinone mass concentration of 430 g / L is 14.5 g / L, the solubility of H2 in the working solution system is 1.56 mmol / L, and the mass transfer factor of H2 is 0.171 s -1 .

[0066] Example 5

[0067] A mixture of C9-C 10 aromatic hydrocarbon / phosphoric acid trioctyl ester / N-phenyl 1-isopropyl-2-tert-butyl imide = 70 / 5 / 25 by volume fraction is used as the solvent system, and the working solution system is subjected to performance evaluation under the process conditions of Example 3. The test results show that the solubility of 2-ethylanthraquinone in the working solution system is 181.8 g / L at 25℃ and normal pressure, the solubility of 2-ethylhydroanthraquinone is 113.7 g / L at 53-60℃ and 0.25-0.30 MPa, the hydrogenation efficiency of the working solution with a 2-ethylanthraquinone mass concentration of 180 g / L is 13.7 g / L, the solubility of H2 in the working solution system is 1.49 mmol / L, and the mass transfer factor of H2 is 0.169 s -1 .

[0068] Example 6

[0069] A mixture of C9-C 10The aromatic hydrocarbon / trioctyl phosphate / N-ethyl 1-benzyl-2-octyl imide = 80 / 10 / 10 mixture was used as the solvent system, 2-ethylanthraquinone working solution was prepared, and the working solution system was evaluated for performance using the process conditions of Example 3. The test results show that the solubility of 2-ethylanthraquinone in the working solution system is 192.8 g / L at 25°C under normal pressure, the solubility of 2-ethylanthraquinone is 99.5-102.1 g / L at 50-60°C under 0.25-0.30 MPa, the hydrogenation efficiency of the working solution with a 2-ethylanthraquinone mass concentration of 190 g / L is 13.6 g / L, the solubility of H2 in the working solution system is 1.52 mmol / L, and the mass transfer factor of H2 is 0.163 s -1 .

[0070] Comparative Example 1

[0071] C9-C 10 The aromatic hydrocarbon / trioctyl phosphate = 75 / 25 mixture was used as the solvent system, 2-ethylanthraquinone working solution was prepared, and the working solution system was analyzed for performance using the conditions of Example 3. The test results show that the solubility of 2-ethylanthraquinone in the C9-C 10 The solubility of 2-ethylanthraquinone in the aromatic hydrocarbon / trioctyl phosphate working solution system is 123-130 g / L, the solubility of 2-ethylanthraquinone is 68.5-70 g / L at 53-60°C under 0.25-0.30 MPa, the hydrogenation efficiency of the working solution with a 2-ethylanthraquinone mass concentration of 125 g / L is 6.5-7.3 g / L, the solubility of H2 in the working solution system is 1.12 mmol / L, and the mass transfer factor of H2 is 0.125 s -1 .

[0072] Comparative Example 2

[0073] The working solution was prepared according to Example 3 of CN1552618A, and the working solution system was analyzed for performance using the conditions of Example 3.

[0074] The test results show that the solubility of hydrogenanthraquinone in the working solution with a 2-ethylanthraquinone mass concentration of 154 g / L is 51.5-53.1 g / L at a temperature of 53-60°C and a pressure of 0.25-0.30 MPa, the hydrogenation efficiency is 7.4-7.8 g / L, the solubility of H2 in the working solution system is 1.27 mmol / L, and the mass transfer factor of H2 is 0.131 s -1 .

[0075] Comparative Example 3

[0076] The aromatic + N-phenyl N-ethyl benzamide (BEA) binary solvent system disclosed in EP0287421 was used to prepare a 2-ethylanthraquinone working solution, and the performance of the working solution system was analyzed under the conditions of Example 3. The test results show that the solubility of 2-ethylanthraquinone in the working solution system is 155-163 g / L at 25°C under normal pressure, the solubility of 2-ethylanthraquinone is 85-89 g / L at 55-60°C under 0.25-0.30 MPa, the hydrogenation efficiency of the working solution with a 2-ethylanthraquinone mass concentration of 150 g / L is 10.33 g / L, the solubility of H2 in the working solution system is 1.30 mmol / L, and the mass transfer factor of H2 is 0.135 s -1 .

Claims

1. A solvent system for the working solution in the production of hydrogen peroxide by the anthraquinone process, characterized in that it comprises The composition comprises the following components: aromatic hydrocarbon, imide derivative A and trioctyl phosphate; wherein the structural formula of the imide derivative A is: wherein R1, R2, R3 are each one of furan, aromatic hydrocarbon substituent, benzyl or alkyl substituent having 1 to 8 carbon atoms; the aromatic hydrocarbon is 30 to 95 parts by volume, the trioctyl phosphate is 2 to 20 parts by volume, and the imide derivative A is 2 to 30 parts by volume.

2. Anthraquinone process for production of hydrogen peroxide working solution solvent system according to claim 1, characterized by, The aromatic hydrocarbon is 60-80 parts, the trioctyl phosphate is 5-15 parts, and the imide derivative A is 5-15 parts in volume parts.

3. The anthraquinone process for production of hydrogen peroxide working solution solvent system as claimed in claim 1 wherein: The furan, aromatic hydrocarbon substituent, benzyl or alkane substituent further contains one or more functional groups of alkyl, alkoxy and ester.

4. Anthraquinone process for the production of hydrogen peroxide working solution solvent system according to claim 1 or 2, characterized by: The aromatic hydrocarbon is C9~C 10 The aromatic hydrocarbon is C9~C R1~R3 in the imide derivative A molecule are respectively one of C2~C6 normal / iso-alkyl substituent groups.

5. A solvent system for the working solution of hydrogen peroxide produced by the anthraquinone process according to claim 4, characterized in that, The synthesis method of the imide derivative A comprises the following steps: (1) dissolving carboxylic acid A and carboxylic acid B in an organic solvent, performing intermolecular dehydration reaction under the action of catalyst A, dehydrating agent A and high temperature conditions, separating the dehydrating agent A after the reaction is completed, then performing extraction separation to obtain inorganic extraction liquid and 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, and then the inorganic phase is separated to obtain an organic solution containing imide D; (3) adding an appropriate amount of halogenated hydrocarbon to the organic solution containing imide D, and performing nucleophilic substitution reaction under weak or strong alkaline conditions, then washing and extracting to obtain an organic extraction phase, removing the solvent by reduced pressure distillation, and drying to obtain the imide derivative product; The catalyst A in step (1) is an aqueous solution of sodium methoxide and ferrous nitrate. The catalyst B and dehydrating agent B in step (2) are a mixed solution of triethylamine and potassium carbonate.

6. The anthraquinone process for production of hydrogen peroxide working solution solvent system as claimed in claim 5 wherein: In the synthesis method of the imide derivative A, the carboxylic acid A in step (1) is R1COOH and the carboxylic acid B is R2COOH, wherein R1 and R2 are one of furan, mono-substituted or multi-substituted aromatic hydrocarbon substituent or benzyl, or straight-chain or branched alkane substituent; and the substituent on the aromatic hydrocarbon substituent or benzyl is one or more of alkyl, alkoxy and ester.

7. The anthraquinone process for production of hydrogen peroxide working solution solvent system as claimed in claim 5 wherein: In the synthesis method of the imide derivative A, the organic solvent in step (1) is selected from one or more of xylene, mesitylene, chlorobenzene, N,N-dimethylformamide, ethyl acetate or pyridine; and the dosage ratio of the organic solvent to the carboxylic acid is 2-10 mL / g.

8. The anthraquinone process for production of hydrogen peroxide working solution solvent system as claimed in claim 5 wherein: In the synthesis method of the imide derivative A, 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.

9. The anthraquinone process for production of hydrogen peroxide working solution solvent system as claimed in claim 5 wherein: In the synthesis method of the imide derivative A, the molar ratio of the 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 anthraquinone process for production of hydrogen peroxide working solution solvent system as claimed in claim 5 wherein: In the synthesis method of the imide derivative A, the dehydration reaction conditions in step (1) are: normal pressure, 40-80℃, and reaction for 18-25 hours.

11. The anthraquinone process for production of hydrogen peroxide working solution solvent system as claimed in claim 5 wherein: In the synthesis method of the imide derivative A, 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.

12. The anthraquinone process for production of hydrogen peroxide working solution solvent system as claimed in claim 5 wherein: In the synthesis method of the imide derivative A, the ammonia source in step (2) is ammonia gas, ammonia water, ammonium bicarbonate or urea, and the feeding molar ratio of the ammonia source to the acid anhydride C is 1.2-10:

1.

13. The anthraquinone process for production of hydrogen peroxide working solution solvent system as claimed in claim 5 wherein: In the synthesis method of the imide derivative A, the low-temperature reaction condition is 2-5 hours of reaction at 25-50 DEG C; and the high-temperature reaction condition is 1-1.5 hours of reaction at 210-230 DEG C.

14. The anthraquinone process for production of hydrogen peroxide working solution solvent system as claimed in claim 5 wherein: In the synthesis method of the imide derivative A, the reaction condition of step (3) is 8-15 hours of reaction at 25-50 DEG C; and the halogenated hydrocarbon is a brominated alkane or a chlorinated alkane.

15. The anthraquinone process for production of hydrogen peroxide working solution solvent system as claimed in claim 5 wherein, The halogenated hydrocarbon is a brominated alkane, and the molar ratio of the halogenated hydrocarbon to the carboxylic acid A is 1.2-1.5:

1.

16. A working solution for hydrogen peroxide production by the anthraquinone process, characterized by: The working liquid solvent system is the working liquid solvent system for producing hydrogen peroxide by the anthraquinone process according to any one of claims 1-15, and the working carrier is one or more of anthraquinone and derivatives thereof.

17. The working solution for hydrogen peroxide production by the anthraquinone process according to claim 16, characterized by that: The working carrier is 2-alkylanthraquinone.

18. A process for hydrogenation of hydrogen peroxide produced by the anthraquinone process, characterized by: The hydrogenation step adopts the working liquid solvent system for producing hydrogen peroxide by the anthraquinone process according to any one of claims 1-15, and the process condition of the hydrogenation step is that the hydrogenation temperature is 25-80 DEG C and the pressure is 0.1-0.7 MPa.

Images