A solvent system for anthraquinone process hydrogen peroxide working solution

Abstract

The application discloses a solvent system for working solution of hydrogen peroxide produced by an anthraquinone method, which comprises the following components: an imide derivative A and an aromatic hydrocarbon, wherein the imide derivative A is 5-60 parts, preferably 10-50 parts, and more preferably 15-35 parts, and the aromatic hydrocarbon is 30-95 parts, preferably 60-80 parts, in volume fraction. The solvent system for working solution of hydrogen peroxide produced by the anthraquinone method has good solubility to anthraquinone and hydrogen anthraquinone, low mutual solubility with water, stable physical and chemical properties, meets the use requirements of the anthraquinone method, can significantly improve the production efficiency of the anthraquinone method for producing hydrogen peroxide, and 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, and the process uses 2-alkyl anthraquinone as a working carrier. 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. The working solution, as the "blood" of the anthraquinone process, has a decisive influence on the production efficiency of each production unit. The mass of H2O2 generated per unit volume of working solution (i.e. the number of grams of H2O2 that can be prepared per liter of working solution) is generally used as an important index for evaluating production capacity. An ideal working liquid solvent system should have the following characteristics: (1) good chemical stability of the solvent, good resistance to hydrogenation, oxidation and hydrolysis; (2) high solubility of anthraquinone and hydrogen anthraquinone; (3) large density difference with water, facilitating the extraction separation of working liquid and water; (4) large interfacial tension, high partition coefficient of H2O2 between H2O and the solvent; (5) low viscosity, high boiling point and flash point; (6) low water solubility of the solvent, low solubility in H2O2 solution; (8) low toxicity.

[0004] 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 anthraquinone solvent is mainly selected from C9~C 10Heavy aromatic hydrocarbon (AR), hydrogen anthraquinone solvent is mainly selected by trioctyl phosphate (TOP), but the existing working fluid solvent system mainly has the following technical problems: (1) The solubility of anthraquinone and hydrogen anthraquinone is low, which leads to low anthraquinone conversion rate, large working fluid circulation amount and small operation flexibility. The solubility of AR / TOP solvent system to 2-ethylanthraquinone is only 130-150 g / L at room temperature, and the solubility of hydrogen anthraquinone is only 55-60 g / L under working conditions. In order to avoid the crystallization of hydrogen anthraquinone leading to the deterioration of the physical and chemical properties of the working fluid, the anthraquinone conversion rate is usually controlled at a low level (generally less than 40%). The solubility of the working fluid to anthraquinone and hydrogen anthraquinone determines the maximum production capacity of the working fluid to hydrogen peroxide. Insufficient solubility of the working fluid is a bottleneck problem that limits the production efficiency. (2) The hydrogenation efficiency of the working fluid is low, which leads to low product concentration of hydrogen peroxide, limits the production efficiency of the device, and the production cost is high. At present, the hydrogenation efficiency of domestic hydrogen peroxide industrial device is generally less than 8.5 g / L. The huge circulation amount of the working fluid in the reaction system meets the production load requirements of the device, which puts forward strict requirements on the load of power equipment and the structure of the reactor. Not only the engineering difficulty is large, but also the energy consumption is high, the investment is large, and the product concentration of hydrogen peroxide is low, which needs to be further purified and concentrated to meet the quality concentration requirements of hydrogen peroxide for processes such as propylene / hydrogen peroxide direct oxidation process for producing epoxy propane (HPPO) and cyclohexanone ammonium oxime process for producing caprolactam. If the hydrogenation efficiency of the working fluid is improved, the circulation amount of the working fluid can be significantly reduced under the same working conditions, and the product purification and concentration process can be avoided, which reduces the production cost and safety hidden danger. (3) The degradation of the working fluid is serious, which leads to low product quality grade of hydrogen peroxide, high consumption of anthraquinone, and cannot meet the demand of high-purity hydrogen peroxide product. The existence of degradation in the working fluid not only causes the loss of effective anthraquinone, increases the consumption of anthraquinone, but also significantly deteriorates the physical and chemical properties of the working fluid, leading to poor fluidity, low interfacial tension, easy overflow of the extraction tower, difficulty of the working fluid to condense in the extraction tower, resulting in water in the raffinate; The viscosity of the working fluid increases, the flow resistance increases, which affects the separation of the extraction tower; The density of the working fluid increases, which reduces the density difference between the working fluid and water, and the working fluid and water are cosolvent in the extraction tower, which leads to difficulty in separation, and further leads to more impurities in the product.

[0005] CN1552618A discloses an aromatic hydrocarbon + trioctyl phosphate + methylcyclohexyl acetate (AR / TOP / MCHA) ternary solvent system based on AR / TOP binary solvent system, compared with the traditional AR / TOP binary system, the solubility of 2-ethylanthraquinone in AR / TOP / MCHA system can be increased by 30 g / L, and the hydrogenation efficiency of working solution can be increased to 9-9.5 g / L. CN1583546A discloses an aromatic hydrocarbon + trioctyl phosphate + tetrabutyl urea (AR / TOP / TBU) ternary solvent system, compared with the traditional AR / TOP binary system, the solubility of hydrogenanthraquinone in AR / TOP / TBU system is increased by about 10%, and the hydrogenation efficiency of working solution is slightly increased. EP0287421 discloses an aromatic hydrocarbon + N-phenyl N-ethyl benzamide (AR / BEA) binary solvent system, although the solubility of anthraquinone and hydrogenanthraquinone in the system is obviously increased, the working solution formed by anthraquinone has high density and high water solubility, which leads to poor separation effect of hydrogen peroxide extraction, high residual carbon in hydrogen peroxide product, and poor application effect, which cannot meet the requirements of industrial application. SUMMARY

[0006] In view of the deficiencies of the prior art, the present application provides a working solution solvent system for producing hydrogen peroxide by anthraquinone method, which has good solubility for anthraquinone and hydrogenanthraquinone, low mutual solubility with water, stable physicochemical properties, and can meet the use requirements of anthraquinone method, improve the production efficiency of anthraquinone method for producing hydrogen peroxide, and has good industrial application prospect.

[0007] The working solution solvent system for producing hydrogen peroxide by anthraquinone method of the present application comprises the following components: imide derivative A and aromatic hydrocarbon, wherein the structural formula of 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, and the furan, aromatic hydrocarbon substituent, benzyl or alkane substituent further contains one or more functional groups of alkyl, alkoxy or ester group; the imide derivative A is 5-60 parts, preferably 10-50 parts, and more preferably 15-35 parts, and the aromatic hydrocarbon is 30-95 parts, preferably 60-80 parts, by volume fraction.

[0008] In the present application, the heavy 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, and the number of carbon atoms of the substituent groups at different positions can be allocated and adjusted according to the different physicochemical property requirements of the working solution, but the total number of carbon atoms is generally not higher than 18.

[0009] The application also provides a working solution for hydrogen peroxide production by anthraquinone method, which comprises an imide derivative A and an aromatic hydrocarbon, 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 application also provides a hydrogenation process for hydrogen peroxide production by anthraquinone method, which adopts the working solution solvent system comprising the imide derivative A and the aromatic hydrocarbon. The process conditions of the hydrogenation step are as follows: hydrogenation temperature 25-80℃, pressure 0.1-0.7MPa, and the hydrogenation reactor can be a fluidized bed, a slurry bed or a fixed bed.

[0011] The hydrogenation catalysts commonly used in the field of anthraquinone method can be used in the hydrogenation step, the hydrogenation active component is generally Pd, the carrier is generally alumina or silica gel, and one or more of the following elements can be added to the catalyst as an auxiliary component, such as Mo, Na, K, Ni, Mg, Au, Ca, Fe, etc., and the content of the hydrogenation active component is 0.05%-5% and the content of the auxiliary component is 0.05%-3% based on the weight of the hydrogenation catalyst component.

[0012] In the application of the working solution for hydrogen peroxide production by anthraquinone method, the oxidation step can adopt 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 25-70℃, pressure 0.1-0.5MPa.

[0013] The synthesis method of the imide derivative A of the 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 conditions. 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) 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 is completed, the inorganic phase is separated out to obtain an organic solution containing imide D;

[0016] (3) A proper 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 application, the intermolecular dehydration reaction formula of step (1) is as follows:

[0018]

[0019] Step (1) is to form a high molecular anhydride C with different structural functional groups by intermolecular dehydration of carboxylic acids A and B containing different or same structural functional groups.

[0020] In the method of the present application, the carboxylic acid A (R1COOH) and carboxylic acid B (R2COOH) in step (1) are furan, mono-substituted or poly-substituted aromatic hydrocarbon substituent or benzyl, or straight-chain or branched alkane substituent; the substituent on the aromatic hydrocarbon substituent or benzyl can be one or more of alkyl, alkoxy, ester, etc.

[0021] 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; the ratio of the amount of organic solvent to carboxylic acid is 2-10 mL / g, preferably 3-6 mL / g.

[0022] In the method of the present application, the catalyst A in 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 in step (1) is 1:1:0.15-0.5:0.5-5.

[0024] In the method of the present application, the dehydration reaction conditions in step (1) are: normal pressure, 240-280℃, 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 reaction process is 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 placed in an oven for drying to obtain the target product white solid.

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

[0026] In the method of the present application, the amination reaction formula in 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 ℃ for 2-5 hours, and the high-temperature reaction condition is 210-230 ℃ 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 in step (2) is preferably added in batches or slowly and dropwise to the mixed solution of the catalyst B and the dehydrating agent B (triethylamine and potassium carbonate), and the addition time is preferably 25-35 minutes.

[0034] 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.

[0035] In the method, the reaction equation in step (3) is as follows (taking bromoalkane as an example):

[0036]

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

[0038] In the method, the drying condition in step (3) is 12-24 hours at 120-140 ℃ under normal pressure.

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

[0040] In the method, the haloalkane in step (3) is bromoalkane, chloroalkane or the like, preferably bromoalkane, and the molar ratio of the haloalkane 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 of anthraquinone and hydrogenanthraquinone, the solubility of 2-alkylanthraquinone in the working solution is more than 180 g / L under normal temperature and pressure, and the solubility of 2-alkylhydroanthraquinone can reach more than 110 g / L under anthraquinone working conditions, which can greatly improve 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 with 2-ethylanthraquinone concentration of 180 g / L and 2-pentylanthraquinone concentration of 350 g / L can reach more than 13.5 g / L and 15 g / L respectively under working conditions; (3) low mutual solubility of the working solution and water, and the residual carbon value in the hydrogen peroxide product is less than 200 ppm. 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 solubility of anthraquinone and hydrogenanthraquinone in different working solution systems is evaluated according to the following process, and the residual carbon index in hydrogen peroxide product is evaluated as follows:

[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 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 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 volume is 1 ml, and chromatographic column temperature is 308.15 K. 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 by 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) 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 taken and analyzed by TOC residual carbon instrument.

[0047] Example 1

[0048] For example, the synthesis process of N-tert-butyl di-tert-butyl imide 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 reactor at one time. The temperature of the system is raised to 265°C. After constant temperature reaction for 20 hours, the reaction is stopped. P2O5 powder is filtered out. The reaction solution is transferred to a Buchner funnel and washed with deionized water for three times. The inorganic aqueous solution is separated. The organic raffinate is returned to the reactor. The mixed gas of ammonia and nitrogen is filled into the reaction system. The pressure is increased to 0.25-0.3 MPa. 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 for 20 min. The temperature of the system is increased to 220°C 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. 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 layer-by-layer analysis (ethyl acetate: n-hexane = 2:1). The composition of the raw materials and products in the reaction system is monitored by TCL. After the reaction is completed, the reaction product is washed with deionized water for three times. The reaction solution is vacuum dehydrated at a vacuum degree of -0.6 to -0.75 MPa. The product is washed with dichloromethane. The solvent is distilled under reduced pressure. The product is placed in an oven for drying 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 spectroscopy, which is confirmed to be N-n-butyl di-tert-butyl imide. The total yield is 95.6% (calculated based on the raw material carboxylic acid).

[0049] 1H NMR (500 MHz, CDC13) 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);

[0050] MS [M+H] + : 241.7.

[0051] Example 2

[0052] 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 reaction raw materials and the use 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 P205, 30 mL of sodium methoxide and a mixed solution of iron salt (5.4 g of sodium methoxide and 9.1 g of ferrous nitrate) were put 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°C 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 the product was washed with dichloromethane. The solvent was distilled under reduced pressure, and the product was placed in an oven for drying for 4 hours. Finally, the white crystal product was obtained. The obtained product was confirmed by 1H NMR and MS spectrum analysis to be N-isopentyl 1-isopropyl-2 tert-butyl imide structure, and the yield was 95.6% (calculated based on the raw material carboxylic acid).

[0053] 1H NMR (500 MHz, CDC13) 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);

[0054] MS [M+H] + : 241.3.

[0055] Example 3

[0056] The content of C9~C 10Aromatic hydrocarbon / N-phenyl 1-isopropyl-2-tert-butyl imide = 75 / 25 mixture as solvent system, 2-pentyl anthraquinone working solution was prepared. The working solution was evaluated by hydrogenation reaction in 500 ml batch stirred reactor, hydrogenation temperature was 45~50℃, hydrogenation pressure was 0.1~0.3 MPa, stirring rate was 300~400 rpm; the obtained hydrogenation liquid was oxidized by air under normal pressure, 30~50℃ for 15~30 min; after the oxidation liquid was extracted by pure water for 4 times, the hydrogen peroxide content in the extract was determined by potassium permanganate titration method, and the hydrogenation efficiency of the working solution was calculated; the catalyst used in hydrogenation experiment was Pd / Al2O3 catalyst commonly used in hydrogen peroxide industry, the particle size was 0.4~0.5 mm, the pore volume was 0.6~0.7 cm 3 / g, the specific surface area was 150~180 m 2 / g, and the Pd content was 0.25~0.30 wt .%.

[0057] The test results show that: the solubility of 2-ethyl anthraquinone in the working solution solvent system is 199.5 g / L at 25℃ under normal pressure, the solubility of 2-ethyl hydrogen anthraquinone is 102.5 g / L at 50~55℃, 0.25~0.28 MPa, the hydrogenation efficiency of the working solution with 2-ethyl anthraquinone mass concentration of 180 g / L is 14.9 g / L, and the organic residual carbon in the hydrogen peroxide product is 155~160 ppm.

[0058] Example 4

[0059] C9~C 10 Aromatic hydrocarbon / N-phenyl 1-isopropyl-2-tert-butyl imide = 75 / 25 mixture as solvent system, 2-pentyl anthraquinone working solution was prepared. The working solution was evaluated by hydrogenation reaction in 500 ml batch stirred reactor, hydrogenation temperature was 45~50℃, hydrogenation pressure was 0.1~0.3 MPa, stirring rate was 300~400 rpm; the obtained hydrogenation liquid was oxidized by air under normal pressure, 30~50℃ for 15~30 min; after the oxidation liquid was extracted by pure water for 4 times, the hydrogen peroxide content in the extract was determined by potassium permanganate titration method, and the hydrogenation efficiency of the working solution was calculated; the catalyst used in hydrogenation experiment was Pd / Al2O3 catalyst commonly used in hydrogen peroxide industry, the particle size was 0.4~0.5 mm, the pore volume was 0.6~0.7 cm

[0060] Example 5

[0061] C9~C 10A 2-ethylanthraquinone working solution was prepared using an 80 / 20 mixture of aromatic hydrocarbons and N-isopentyl-1-isopropyl-2-benzylimide as the solvent system. The performance of this working solution system was evaluated under the process conditions of Example 3. The test results showed that the solubility of 2-ethylanthraquinone in the working solution system was 188.3 g / L at 25°C and atmospheric pressure, and 105.8 g / L at 53–60°C and 0.25–0.30 MPa. The hydrogenation efficiency of the working solution with a 2-ethylanthraquinone mass concentration of 180 g / L was 13.7 g / L, and the organic residual carbon in the hydrogen peroxide product was 145–152 ppm.

[0062] Example 6

[0063] Measured by volume fraction, in C9~C 10 A 60 / 40 mixture of aromatic hydrocarbons and N-ethyl-1-alkoxy-2-heptaylimide was used as the solvent system to prepare a 2-ethylanthraquinone working solution. The performance of this working solution system was evaluated using the process conditions of Example 3. The test results showed that the solubility of 2-ethylanthraquinone in the working solution system was 190.5 g / L at 25°C and atmospheric pressure; the solubility of 2-ethylhydroanthraquinone was 102.5–103 g / L at 50–60°C and 0.25–0.30 MPa; the hydrogenation efficiency of the working solution with a 2-ethylanthraquinone mass concentration of 185 g / L was 14.8 g / L; and the organic residual carbon in the hydrogen peroxide product was 150–160 ppm.

[0064] Example 7

[0065] Measured by volume fraction, in C9~C 10 A 70 / 30 mixture of aromatic hydrocarbons and N-ethyl-1-benzyl-2-octylimide was used as the solvent system to prepare a 2-pentylanthraquinone working solution. The performance of this working solution system was evaluated using the process conditions of Example 3. The test results showed that the solubility of 2-pentylanthraquinone in the working solution system was 496.5 g / L at 25°C and normal pressure; the solubility of 2-pentylhydroanthraquinone was 135.9–142.5 g / L at 60–70°C and 0.25–0.30 MPa; the hydrogenation efficiency of the working solution with a 2-pentylanthraquinone mass concentration of 480 g / L was 15.3 g / L; and the organic residual carbon in the hydrogen peroxide product was 141–154 ppm.

[0066] Comparative Example 1

[0067] Measured by volume fraction, in C9~C 10 A 75 / 25 mixture of aromatic hydrocarbons and trioctyl phosphate was used as the solvent system to prepare a 2-ethylanthraquinone working solution. The performance of this working solution system was analyzed under the conditions of Example 1. The experimental results show that 2-ethylanthraquinone, under 25°C and normal pressure, exhibits good performance at C9~C60°C. 10The solubility in the aromatic hydrocarbon / trioctyl phosphate working solution system is 123-130 g / L, the solubility of 2-ethylhydroanthraquinone is 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 a 2-ethylanthraquinone mass concentration of 125 g / L is 6.5-7.3 g / L, and the organic residual carbon in the hydrogen peroxide product is 205 ppm.

[0068] Comparative Example 2

[0069] The working solution was prepared according to Example 3 of CN1552618A, and the performance of the working solution system was analyzed under the conditions of Example 1.

[0070] The test results show that under the conditions of a temperature of 53-60℃ and a pressure of 0.25-0.30 MPa, the solubility of 2-ethylanthraquinone in the working solution with a mass concentration of 154 g / L is 51.5-53.1 g / L, the hydrogenation efficiency is 7.4-7.8 g / L, and the organic residual carbon in the hydrogen peroxide is 351 ppm.

[0071] Comparative Example 3

[0072] The working solution of 2-ethylanthraquinone was prepared according to the aromatic hydrocarbon+N-phenyl N-ethylbenzamide (BEA) binary solvent system disclosed in EP0287421, and the performance of the working solution system was analyzed under the conditions of Example 1. The test results show that the solubility of 2-ethylanthraquinone in the working solution system is 155-163 g / L under the conditions of 25℃ and normal pressure, the solubility of 2-ethylhydroanthraquinone is 85-89 g / L under the conditions of 55-60℃ and 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, and the organic residual carbon in the hydrogen peroxide product is 554.8 ppm.

Claims

1. A solvent system for producing hydrogen peroxide working solution via the anthraquinone process, characterized in that... It includes the following components: imide derivative A and aromatic hydrocarbon, wherein the structure 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, imide derivative A is 5 to 60 parts and aromatic hydrocarbon is 30 to 95 parts.

2. The solvent system for producing hydrogen peroxide using the anthraquinone process according to claim 1, characterized in that, The imine derivative A is 10-50 parts by volume, and the aromatic hydrocarbon is 60-80 parts.

3. The solvent system for producing hydrogen peroxide using the anthraquinone process according to claim 1, characterized in that, The imine derivative A is 15-35 parts by volume, and the aromatic hydrocarbon is 60-80 parts.

4. The solvent system for producing hydrogen peroxide using the anthraquinone process 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.

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

6. The solvent system for producing hydrogen peroxide using the anthraquinone process according to any one of claims 1 to 5, characterized in that: (1) Dissolve carboxylic acid A and carboxylic acid B in an organic solvent and carry 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 extracted 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) Add an appropriate amount of haloalkanes to the organic solution containing imide D and carry out a nucleophilic substitution reaction under weak or strong alkaline conditions. After the reaction, wash and extract to obtain an organic extract phase, remove the solvent by vacuum distillation, and dry to obtain an imide derivative product.

7. The solvent system for producing hydrogen peroxide using the anthraquinone process according to claim 6, characterized in that: In the method for synthesizing imide derivative A, carboxylic acid A (R1COOH) and carboxylic acid B (R2COOH) in step (1) are respectively furan, a mono- or poly-substituted aromatic hydrocarbon substituent or benzyl, or a 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.

8. The solvent system for producing hydrogen peroxide using the anthraquinone process according to claim 6, 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.

9. The solvent system for producing hydrogen peroxide using the anthraquinone process according to claim 6, characterized in that: The method for synthesizing imide derivative A is characterized in that: 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.

10. The solvent system for producing hydrogen peroxide using the anthraquinone process according to claim 6, 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.

11. The solvent system for producing hydrogen peroxide using the anthraquinone process according to claim 6, characterized in that: In the synthesis method of imide derivative A, the dehydration reaction conditions in step (1) are: atmospheric pressure, 240~280℃ for 18~25 hours.

12. The solvent system for producing hydrogen peroxide using the anthraquinone process according to claim 6, characterized in that: In the synthesis method of imide derivative A, the ammonolysis reaction in step (2) is as follows: 。 13. The solvent system for producing hydrogen peroxide using the anthraquinone process according to claim 6, 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.

14. The solvent system for producing hydrogen peroxide using the anthraquinone process according to claim 6, 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.

15. The solvent system for producing hydrogen peroxide using the anthraquinone process according to claim 6, characterized in that: In the synthesis method of imide derivative A, the low-temperature reaction conditions are: 25~50 °C for 2~5 hours; the high-temperature reaction conditions are: 210~230 °C for 1~1.5 hours.

16. The solvent system for producing hydrogen peroxide using the anthraquinone process according to claim 6, 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.

17. The solvent system for producing hydrogen peroxide using the anthraquinone process according to claim 6, characterized in that, The haloalkanes mentioned are bromoalkanes.

18. A working solution for producing hydrogen peroxide via the anthraquinone process, characterized in that: The solvent system of the working solution is the solvent system of the hydrogen peroxide production working solution produced by the anthraquinone method as described in any one of claims 1-17, and the working carrier is one or more of anthraquinone and its derivatives.

19. The anthraquinone process for producing hydrogen peroxide working solution according to claim 18, characterized in that: The working carrier of this working fluid is 2-alkylanthraquinone.

20. A hydrogenation process for producing hydrogen peroxide using the anthraquinone method, characterized in that: The hydrogenation step uses the anthraquinone process described in any one of claims 1-17 to produce the working solution solvent system for hydrogen peroxide; the process conditions for the hydrogenation step are: hydrogenation temperature 25-80℃, pressure 0.1-0.7MPa.

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