Hydrogenated liquid treatment device for producing hydrogen peroxide by anthraquinone method

Abstract

The invention discloses a hydrogenated liquid treatment device for producing hydrogen peroxide by an anthraquinone process. The hydrogenated liquid treatment device comprises a hydrogenation reaction unit, a hydrogenated liquid tank, a washing unit and a hydrogenated liquid pump which are connected in sequence, and an acid liquid feeding opening is formed in a hydrogenated liquid discharging pipeline of the washing unit; the washing unit is provided with a washing water feeding pipeline, and a pure water feeding port is formed in the washing water feeding pipeline. According to the hydrogenation liquid treatment device, washing is adopted to replace existing secondary and tertiary filters, so that the content of metal ion impurities in hydrogenation liquid entering the oxidation tower can be remarkably reduced, the oxidation yield is increased, and the stability of extraction liquid is improved.

Description

Technical Field

[0001] The present invention relates to a process for producing hydrogen peroxide by anthraquinone method, and in particular to a hydrogenation liquid treatment device for producing hydrogen peroxide by anthraquinone method. Background Art

[0002] Hydrogen peroxide is a green oxidant widely used in the chemical industry. Currently, hydrogen peroxide is generally produced industrially using the anthraquinone process. In this process, a carrier and solvent are combined in a specific ratio to form a working fluid. Typically, the carrier is 2-ethylanthraquinone, 2-butylanthraquinone, 2-pentylanthraquinone, or a mixture thereof, and the solvent is a mixture of heavy aromatic hydrocarbons, trioctyl phosphate, o-methylcyclohexyl acetate, and tetrabutyl urea. The working fluid circulates through the system in the order of hydrogenation, oxidation, extraction, and post-processing, producing hydrogen peroxide. In the hydrogenation step, the working fluid undergoes a hydrogenation reaction over a catalyst to produce a hydrogenated solution. In the oxidation step, the hydrogenated solution reacts with oxygen to produce an oxidized solution. In the extraction step, the hydrogen peroxide in the oxidized solution is extracted with water to produce crude hydrogen peroxide. The working fluid exiting the extraction step is called the raffinate. In the post-processing step, the raffinate undergoes dehydration, hydrogen peroxide removal, and degradation product regeneration before entering a circulating working fluid storage tank, completing the cycle.

[0003] In the hydrogenation process, either a fixed bed or a gas-liquid-solid three-phase fluidized bed can be used for the hydrogenation reaction, and the catalyst used is generally a palladium / alumina catalyst. In the fluidized bed process, to prevent catalyst loss, a filter is required to capture the catalyst powder in the hydrogenated liquid before it enters the oxidation process. Typically, a primary filter is used to retain the majority of catalyst particles within the fluidized bed reactor. A secondary filter is then installed to intercept catalyst fines that may pass through the primary filter element (CN107032303A). Alternatively, a third or fourth stage filter (CN104549065B) with higher filtration accuracy can be used to further prevent catalyst fines from entering the subsequent oxidation process.

[0004] The aforementioned multi-stage filtration process presents the following challenges: The high-flux filters currently used in industry have limited filtration accuracy, typically up to approximately 0.5 μm. However, the palladium crystals in the catalyst used for anthraquinone hydrogenation are even finer, measuring only 1–10 nm. If palladium crystals shed from the palladium catalyst, three-stage filtration will not effectively prevent them. In fixed-bed processes, the supported palladium metal may also gradually shed over time. In addition to fine catalyst particles and palladium crystals from the palladium catalyst, other metals such as iron and chromium are present in the equipment and pipelines, and aluminum, sodium, and potassium are present in the activated alumina from the post-processing process. These metals may exist in the working fluid as tiny particles or even ions, making them difficult to remove by filtration. Excessive amounts of these metals in the oxidation process can cause hydrogen peroxide decomposition, resulting in low oxidation yields. In co-current oxidation processes, this can also produce excessive residual oxidation liquid. Excessive amounts of these metals in the extraction process can destabilize the extract and, in severe cases, create an explosion risk.

[0005] As the filter element is used for a longer time, the pressure difference before and after the secondary and tertiary filters becomes higher and higher, and the filter element needs to be replaced regularly. A large amount of working fluid components adhere to the filter element and can only be treated as hazardous waste, which increases costs. Summary of the Invention

[0006] To address the above-mentioned problems, the present invention provides a hydrogenated liquid treatment device for producing hydrogen peroxide using the anthraquinone process. The hydrogenated liquid treatment device uses water washing to replace the existing secondary and tertiary filters, which can significantly reduce the metal ion impurity content of the hydrogenated liquid entering the oxidation tower, improve the oxidation yield, and enhance the stability of the extract.

[0007] The present invention adopts the following technical solutions to solve the above problems: A hydrogenation liquid processing device for producing hydrogen peroxide by an anthraquinone process comprises a hydrogenation reaction unit 1, a hydrogenation liquid tank 2, a water washing unit 3, a hydrogenation liquid pump 4, and a coalescer 5 connected in sequence. An acid liquid feeding port 14 is provided on the hydrogenation liquid discharge pipe of the water washing unit 3; a washing water feeding pipe 9 is provided on the washing water feeding pipe 9, and a pure water feeding port 11 is provided on the washing water feeding pipe 9.

[0008] Preferably, the hydrogenated liquid treatment device is provided with a coalescer 5 , and the coalescer 5 is connected to the hydrogenated liquid pump 4 .

[0009] Preferably, the hydrogenated liquid treatment device is provided with a washing water filter unit 6 , the water washing unit 3 is provided with a washing water discharge pipe 8 connected to the washing water filter unit 6 , and a washing water feed pipe 9 is connected to the washing water filter unit 6 .

[0010] Preferably, the hydrogenated liquid treatment device is provided with a washing water treatment unit 7, and the washing water filtration unit 6 is connected to the washing water treatment unit 7. The washing water treatment unit 7 adopts one of chemical precipitation, solvent extraction, adsorption, biological method, reverse osmosis and the like.

[0011] The hydrogenated liquid flowing out of the hydrogenation liquid tank 2 enters the water washing unit 3, where the washing water removes impurities carried by the hydrogenated liquid. The hydrogenated liquid flowing out of the water washing unit 3 is mixed with acid added through the acid liquid feed port 14, then enters the coalescer 5 to remove free water. The hydrogenated liquid flowing out of the coalescer 5 then enters the oxidation process. The washing water flowing out of the water washing unit 3 passes through the washing water discharge pipe 8 and enters the washing water filtration unit 6 for filtration to remove impurities. A portion of the washing water is then mixed with pure water supplied from the pure water feed port 11 through the washing water feed pipe 9 and enters the water washing unit 3 for further use. The remaining portion enters the washing water treatment unit 7.

[0012] Preferably, the hydrogenation reaction unit 1 is a fixed bed reaction unit or a gas-liquid-solid three-phase fluidized bed reaction unit. The fixed bed reaction unit includes a fixed bed reactor and a gas-liquid separator connected to the fixed bed reactor, and the gas-liquid-solid three-phase fluidized bed reaction unit includes a gas-liquid-solid three-phase fluidized bed reactor and a primary filter connected to the gas-liquid-solid three-phase fluidized bed reactor.

[0013] Preferably, the water washing unit 3 can be a stirred tank, a fiber membrane contactor, a sieve plate column, a packed column, or a static mixer. The fiber membrane contactor is a contactor filled with curved fiber filaments, which have been subjected to a hydrophilic treatment. The fiber filaments are made of at least one of stainless steel, polytetrafluoroethylene, polypropylene, polyurethane, polyvinyl chloride, and polyester, preferably stainless steel.

[0014] Preferably, a conductivity monitoring point 12 is provided on the wash water feed pipe 9 at the location after the water is mixed with the pure water supplied from the pure water feed port 11. The flow rate from the wash water filter unit 6 to the wash water treatment unit 7 is controlled based on the monitoring results of the conductivity monitoring point 12. The higher the monitoring results of the conductivity monitoring point 12, the higher the flow rate from the wash water filter unit 6 to the wash water treatment unit 7. The flow rate of the replenished pure water is controlled to achieve a ratio of 10 to 100 for the flow rate of hydrogenated liquid entering the wash unit 3 and the flow rate of wash water entering the wash unit 3 through the wash water feed pipe 9. The conductivity at the conductivity monitoring point is controlled to be 0.1 to 1 μS / cm.

[0015] Preferably, the pure water supplied to the pure water feed port 11 is deoxygenated.

[0016] Preferably, the hydrogenation liquid tank 2 is provided with a gas outlet 15, through which the gas dissolved in the hydrogenation liquid can escape.

[0017] The water treated by the washing water treatment unit 7 can be directly used as supplementary pure water after passing the conductivity test (≤0.5 μS / cm).

[0018] The acid solution is one of a phosphoric acid aqueous solution, a nitric acid aqueous solution, and a mixed aqueous solution of phosphoric acid and nitric acid.

[0019] Compared with the prior art, the present invention has the following beneficial effects: (1) Reduce the amount of hazardous waste generated. In the traditional process using multi-stage filters, the filter elements of the secondary and tertiary filters are replaced regularly. The filter elements adhere to a large amount of working fluid components and are generally treated as hazardous waste. The present invention uses a water washing unit + washing water filtration unit instead. The washing water flow rate is much smaller than the hydrogenation liquid flow rate, thereby reducing the number of filter element replacements in the filter. The replaced filter elements are general solid waste, reducing the hazardous waste treatment costs of the production enterprise; (2) Reduce the amount of residual oxidation liquid produced. Add a hydrogenation liquid coalescer to significantly reduce the free water content in the hydrogenation liquid before it enters the oxidation tower. The excess acid added due to misoperation will also be removed, thereby reducing the amount of residual oxidation liquid generated in the parallel flow oxidation tower. (3) Improve the safety of the device. Eliminate the secondary and tertiary filters. Since impurities such as catalyst fines, metal grains, and metal ions are more likely to enter the water phase, the water washing method can more thoroughly remove the metal ion impurities in the working fluid. For example, when the hydrogenation liquid or the circulating working fluid is regenerated, an alkaline treatment process is used. Even if a small amount of alkaline substances are brought into the hydrogenation process, they can be completely removed in the hydrogenation liquid water washing step, completely eliminating the possibility that the oxidation liquid is alkaline. (4) It is conducive to the stable operation of the oxidation process. The palladium catalyst used in the hydrogenation process and the regeneration agent used in the regeneration unit (activated alumina, potassium carbonate, sodium hydroxide, etc.) may introduce metal impurities into the working fluid. Setting up water washing in the hydrogenation fluid can significantly reduce the content of metal impurities entering the oxidation process, improve the oxidation yield, and reduce oxidative degradation; (5) Improve the quality of the extract. Reduce the content of metal impurities in the extract and improve the stability of the extract. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] Figure 1 A hydrogenated liquid processing device for producing hydrogen peroxide by the anthraquinone method of the present invention; In the figure, 1 is the hydrogenation reaction unit, 2 is the hydrogenation liquid tank, 3 is the water washing unit, 4 is the hydrogenation liquid pump, 5 is the coalescer, 6 is the washing water filtration unit, 7 is the washing water treatment unit, 8 is the washing water discharge pipe, 9 is the washing water feed pipe, 11 is the pure water feed port, 12 is the conductivity monitoring site, 14 is the acid liquid feeding port, and 15 is the gas outlet. DETAILED DESCRIPTION

[0021] The analytical method for the stability of the extract was based on GBT1616-2014.

[0022] The metal ion content in the hydrogenated liquid was determined by ICP-OES.

[0023] In the examples and comparative examples, the fluidized bed catalyst for the hydrogenation reaction was a palladium / alumina microspherical catalyst (Liming Chemical, Q / LMY 147-2024) with an average particle size of 60 to 100 μm; the fixed bed catalyst was a palladium / alumina spherical catalyst (Liming Chemical, Q / LMY 127-2020, APC-Q-1S) with an average particle size of 2 to 3 mm.

[0024] Comparative Example 1

[0025] In a 20,000-ton (27.5% capacity) anthraquinone-based hydrogen peroxide fluidized bed system, the catalyst-laden hydrogenation liquid, after exiting the gas-liquid-solid three-phase fluidized bed reactor, enters a primary filter, where the catalyst is intercepted and backwashed back into the fluidized bed reactor with the hydrogenation liquid. The hydrogenation liquid exiting the primary filter passes through a hydrogenation liquid tank, a hydrogenation liquid pump, a secondary filter, and a tertiary filter before entering the oxidation process. The oxidized liquid then enters the extraction process to produce an extract. The oxidation process utilizes a co-current oxidation process. A phosphoric acid solution is added before the hydrogenation liquid pump.

[0026] Three secondary filters were installed, two in service and one as a backup. Each filter was loaded with 50 filter cartridges. Due to the pressure differential between the filters increasing to ~100 kPa, the filter cartridges in one filter were replaced every three months. Three tertiary filters were installed, two in service and one as a backup. Each filter was loaded with 50 filter cartridges. Due to the pressure differential between the filters increasing to ~100 kPa, the filter cartridges in one filter were replaced every six months. The filter cartridges in the secondary and tertiary filters each measure Φ80*1000 mm. Removed filter cartridges are treated as hazardous waste.

[0027] In the oxidation process, the oxidation yield is ~92%, the amount of oxidation residual liquid produced is ~15kg / d, and the stability of the extract is ~90%.

[0028] The hydrogenated liquid was taken from the hydrogenated liquid tank and analyzed for metal ion content. The concentrations of palladium, iron, chromium, aluminum, potassium and sodium ions were all between 1000 and 2000 μg / kg.

[0029] Comparative Example 2

[0030] In a 20,000-ton (27.5% capacity) anthraquinone-based hydrogen peroxide fluidized bed system, the catalyst-laden hydrogenated liquid, after exiting the three-phase fluidized bed reactor, enters a primary filter, where the catalyst is intercepted and backwashed back into the fluidized bed reactor with the hydrogenated liquid. The hydrogenated liquid exiting the primary filter passes through a hydrogenated liquid tank, a hydrogenated liquid pump, a secondary filter, and a tertiary filter before entering the oxidation process. The oxidized liquid then enters the extraction process to produce the extract. The oxidation process utilizes a countercurrent oxidation process. Dilute nitric acid aqueous solution is added before the hydrogenated liquid pump.

[0031] Three secondary filters are installed, two in service and one as a backup. Each filter is loaded with 50 filter cartridges. Due to the pressure differential between the filters increasing to ~100 kPa, all filter cartridges in one filter are replaced every three months. Three tertiary filters are installed, two in service and one as a backup. Each filter is loaded with 50 filter cartridges. Due to the pressure differential between the filters increasing to ~100 kPa, all filter cartridges in one filter are replaced every six months. The individual filter cartridges in the secondary and tertiary filters measure Φ80*1000 mm. Removed filter cartridges are treated as hazardous waste.

[0032] In the oxidation process, the oxidation yield is ~94%, no oxidation residue is produced, and the extract stability is ~88%.

[0033] The hydrogenated liquid coming out of the three-stage filter was taken and analyzed for metal ion content. The concentrations of palladium, iron, chromium, aluminum, potassium, and sodium ions were all between 1500 and 2000 μg / kg.

[0034] Comparative Example 3

[0035] In a 20,000-ton (27.5% capacity) anthraquinone-based fixed-bed hydrogen peroxide production plant, the catalyst-carrying hydrogenated liquid, after exiting the fixed-bed reactor, passes through a gas-liquid separator, a fixed-bed primary hydrogenation filter, and a fixed-bed secondary hydrogenation filter before entering the hydrogenation liquid tank. The hydrogenated liquid from the hydrogenation liquid tank is pumped into the oxidation process, where it then enters the extraction process to produce the extract. The oxidation process utilizes a co-current oxidation process. Aqueous phosphoric acid solution is added before the hydrogenation liquid pump. Dissolved gas in the hydrogenated liquid escapes through the gas outlet at the top of the hydrogenation liquid tank.

[0036] Three fixed-bed hydrogenation primary filters were installed, two in use and one in reserve. Each filter was loaded with 50 filter cartridges. Due to the pressure differential between the filters increasing to ~100 kPa, the filter cartridges in one filter were replaced every three months. Three fixed-bed hydrogenation secondary filters were installed, two in use and one in reserve. Each filter was loaded with 50 filter cartridges. Due to the pressure differential between the filters increasing to ~100 kPa, the filter cartridges in one filter were replaced every six months. The filter cartridges in the secondary and tertiary filters each measured Φ80*1000 mm. Removed filter cartridges were disposed of as hazardous waste.

[0037] In the oxidation process, the oxidation yield is ~92%, the amount of oxidation residual liquid produced is ~10kg / d, and the stability of the extract is ~92%.

[0038] The hydrogenated liquid was taken from the hydrogenated liquid tank and analyzed for metal ion content. The concentrations of palladium, iron, chromium, aluminum, potassium, and sodium ions were all between 400 and 1200 μg / kg.

[0039] Example 1

[0040] The hydrogenation process of a 20,000-ton (27.5% capacity) anthraquinone-based hydrogen peroxide fluidized bed unit includes a gas-liquid-solid three-phase fluidized bed reactor, a primary filter, a hydrogenation liquid tank, a water wash unit, a coalescer, a wash water filter unit, and a wash water treatment unit. After the catalyst-laden hydrogenation liquid exits the three-phase fluidized bed reactor, it enters the primary filter, where the catalyst is intercepted and backwashed back into the fluidized bed reactor with the hydrogenation liquid. The hydrogenation liquid exiting the primary filter enters the hydrogenation liquid tank. After releasing dissolved gas from the gas outlet, it enters the water wash unit, where wash water removes impurities entrained in the hydrogenation liquid. The hydrogenation liquid exits the water wash unit, mixes with acid, and then enters a coalescer to remove free water. The hydrogenation liquid exiting the coalescer enters the oxidation process, where it enters the extraction process to produce an extract. The washing water flowing out of the water washing unit enters the washing water filter unit through the washing water discharge pipe to filter and remove impurities therein. A part of it is mixed with the pure water replenished from the pure water feed port through the washing water feed pipe and then enters the water washing unit for continued use, and the other part enters the washing water treatment unit.

[0041] The water washing unit uses a fiber membrane contactor, which is a contactor filled with curved fiber filaments that have been hydrophilically treated and is made of stainless steel.

[0042] A conductivity monitoring point is located where the wash water feed pipe mixes with the pure water supplied from the pure water inlet. The flow rate from the wash water filtration unit to the wash water treatment unit is controlled based on the conductivity monitoring point's readings. A higher conductivity monitoring point indicates a higher flow rate into the wash water treatment unit. The flow rate of the replenished pure water is controlled to achieve a 50 / 1 ratio between the flow rate of hydrogenated liquid entering the wash unit and the flow rate of wash water entering the wash unit through the wash water feed pipe. The conductivity at the conductivity monitoring point is controlled at 0.5 μS / cm.

[0043] The washing water treatment unit adopts an ammonium chloride chemical precipitation method.

[0044] The added pure water is deoxygenated and the gas dissolved in the hydrogenation liquid escapes from the gas outlet of the hydrogenation liquid tank.

[0045] The water treated by the washing water treatment unit can be directly used as supplementary pure water after passing the conductivity test (≤0.5μS / cm).

[0046] The acid solution is a dilute nitric acid aqueous solution. The hydrogenated liquid at the outlet of the water washing unit can be kept neutral, and the acidity of the hydrogenated liquid at the outlet of the coalescer is 1-3 mg / L.

[0047] The wash water filtration unit contains two wash water filters, one in use and one as a backup. Each filter is loaded with 10 filter cartridges (each measuring Φ80 x 1000mm). All filter cartridges in one filter are replaced every two years on average, when the pressure differential across the filter increases to ~100kPa. Removed filter cartridges are considered ordinary solid waste.

[0048] The oxidation process uses a countercurrent oxidation process. The oxidation yield is ~98%, no oxidation residue is produced, and the extract stability is ~97%.

[0049] The hydrogenated liquid was taken from the hydrogenated liquid discharge pipe of the water washing unit and the metal ion content thereof was analyzed. The concentrations of palladium, iron, chromium, aluminum, potassium and sodium ions were all ≤10 μg / kg.

[0050] Example 2

[0051] The ratio of the flow rate of hydrogenated liquid entering the water wash unit to the flow rate of wash water entering the water wash unit through the wash water feed line was 10 / 1. The conductivity at the conductivity monitoring point was controlled at 0.1 μS / cm. The water wash unit utilized a stirred tank. The wash water treatment unit utilized an acidic organophosphorus solvent extraction method.

[0052] The acid solution is a mixed aqueous solution of phosphoric acid and nitric acid. The hydrogenated liquid at the outlet of the water washing unit can be kept neutral, and the acidity of the hydrogenated liquid at the outlet of the coalescer is 1-3 mg / L.

[0053] The wash water filtration unit contains two wash water filters, one in use and one as a backup. Each filter is loaded with 20 filter cartridges (each measuring Φ80 x 1000mm). All filter cartridges in one filter are replaced every three years on average, when the pressure differential across the filter increases to ~100kPa. Removed filter cartridges are considered ordinary solid waste.

[0054] The parallel flow oxidation process is adopted in the oxidation process.

[0055] The rest is the same as Example 1.

[0056] Oxidation yield ~98%, oxidation residue ~2kg / d, extract stability ~99%.

[0057] The hydrogenated liquid was taken from the hydrogenated liquid discharge pipe of the water washing unit and the metal ion content thereof was analyzed. The concentrations of palladium, iron, chromium, aluminum, potassium and sodium ions were all ≤10 μg / kg.

[0058] Example 3

[0059] The ratio of the flow rate of hydrogenated liquid entering the water wash unit to the flow rate of wash water entering the water wash unit through the wash water feed line is 100 / 1. The conductivity at the conductivity monitoring point is controlled at 1 μS / cm. The water wash unit uses a static mixer. The wash water treatment unit uses activated carbon adsorption.

[0060] The acid solution is a mixed aqueous solution of phosphoric acid and nitric acid. The hydrogenated liquid at the outlet of the water washing unit can be kept neutral, and the acidity of the hydrogenated liquid at the outlet of the coalescer is 1-3 mg / L.

[0061] The wash water filtration unit contains two wash water filters, one in use and one as a backup. Each filter is equipped with five filter cartridges (each measuring Φ80*1000mm). On average, all filter cartridges in one filter are replaced every two years when the pressure differential across the filter increases to ~100kPa. Removed filter cartridges are considered ordinary solid waste.

[0062] The rest is the same as Example 1.

[0063] Oxidation yield ~98%, no oxidation residue, extract stability ~98%.

[0064] The hydrogenated liquid was taken from the hydrogenated liquid discharge pipe of the water washing unit and the metal ion content thereof was analyzed. The concentrations of palladium, iron, chromium, aluminum, potassium and sodium ions were all ≤10 μg / kg.

[0065] Example 4

[0066] In a 20,000-ton (27.5% capacity) anthraquinone-based fixed-bed hydrogen peroxide production plant, the catalyst-carrying hydrogenated liquid, after exiting the fixed-bed reactor, passes through a gas-liquid separator and enters the hydrogenated liquid tank. After the dissolved gas is released from the hydrogenated liquid tank's gas outlet, the hydrogenated liquid enters a water wash unit, where wash water removes impurities carried by the hydrogenated liquid. The hydrogenated liquid, flowing out of the water wash unit, mixes with acid before entering the oxidation process. The oxidized liquid then enters the extraction process to produce an extract. The wash water from the water wash unit flows through a wash water discharge pipe into a wash water filtration unit, where impurities are removed. A portion of the wash water is then mixed with pure water supplied from the pure water inlet through a wash water feed pipe and then enters the water wash unit for further use. The remaining portion enters a wash water treatment unit.

[0067] A conductivity monitoring point is located in the wash water feed pipeline, where the pure water supplied from the pure water inlet mixes. The flow rate from the wash water filtration unit to the wash water treatment unit is controlled based on the conductivity monitoring point's readings. A higher conductivity monitoring point indicates a higher flow rate into the wash water treatment unit. The flow rate of supplemental pure water is controlled to achieve a 20 / 1 ratio between the flow rate of hydrogenated liquid entering the wash unit and the flow rate of wash water entering the wash unit through the wash water feed pipeline. The conductivity at the conductivity monitoring point is controlled at 0.2 μS / cm.

[0068] The water washing unit adopts a sieve plate tower. The washing water treatment unit adopts a single-cell yeast biological treatment method. The hydrogenated liquid at the outlet of the water washing unit can be kept neutral.

[0069] The added pure water is deoxygenated and the gas dissolved in the hydrogenation liquid escapes from the gas outlet of the hydrogenation liquid tank.

[0070] The water treated by the washing water treatment unit can be directly used as supplementary pure water after passing the conductivity test (≤0.5μS / cm).

[0071] The acid solution is a dilute nitric acid aqueous solution. The hydrogenated liquid at the outlet of the water washing unit can be kept neutral.

[0072] The wash water filtration unit contains two wash water filters, one in use and one as a backup. Each filter is loaded with 10 filter cartridges (each measuring Φ80 x 1000mm). All filter cartridges in one filter are replaced every two years on average, when the pressure differential across the filter increases to ~100kPa. Removed filter cartridges are considered ordinary solid waste.

[0073] The acid solution is a mixed aqueous solution of phosphoric acid and nitric acid. After the hydrogenated liquid flowing out of the water washing unit is mixed with the acid solution, the hydrogenated liquid has an acidity of 1-3 mg / L and enters the oxidation process directly without passing through the coalescer.

[0074] The parallel flow oxidation process is adopted in the oxidation process.

[0075] Oxidation yield ~97%, oxidation residue ~10kg / d, extract stability ~96.5%.

[0076] The hydrogenated liquid was taken from the hydrogenated liquid discharge pipe of the water washing unit and the metal ion content thereof was analyzed. The concentrations of palladium, iron, chromium, aluminum, potassium and sodium ions were all ≤10 μg / kg.

[0077] Example 5

[0078] The ratio of the flow rate of hydrogenated liquid entering the water washing unit to the flow rate of washing water entering the water washing unit through the washing water feed pipe is 70 / 1. The conductivity at the conductivity monitoring point is controlled at 0.3 μS / cm.

[0079] The water washing unit adopts a packed tower. The washing water treatment unit adopts an ion exchange resin adsorption method.

[0080] The acid solution is a phosphoric acid aqueous solution. The hydrogenated liquid at the outlet of the hydrogenated liquid washing unit can be kept neutral, and the acidity of the hydrogenated liquid at the outlet of the hydrogenated liquid coalescer is 1-3 mg / L.

[0081] The wash water filtration unit contains two wash water filters, one in use and one as a backup. Each filter is equipped with eight filter cartridges (each measuring Φ80 x 1000mm). On average, all filter cartridges in one filter are replaced every two years when the pressure differential across the filter increases to ~100kPa. Removed filter cartridges are considered ordinary solid waste.

[0082] The hydrogenated liquid flowing out of the water washing unit is mixed with the acid liquid and directly enters the oxidation process without passing through the coalescer.

[0083] The rest is the same as Example 1.

[0084] The oxidation yield is ~96.5%, there is no oxidation residue, and the stability of the extract is ~95%.

[0085] The hydrogenated liquid was taken from the hydrogenated liquid discharge pipe of the water washing unit and the metal ion content thereof was analyzed. The concentrations of palladium, iron, chromium, aluminum, potassium and sodium ions were all ≤10 μg / kg.

[0086] Example 6

[0087] The ratio of the flow rate of hydrogenated liquid entering the water wash unit to the flow rate of washing water entering the water wash unit through the washing water feed pipe is 30 / 1. The conductivity at the conductivity monitoring point is controlled at 0.7 μS / cm.

[0088] The water washing unit adopts a static mixer. The washing water treatment unit adopts a reverse osmosis method.

[0089] The acid solution is a phosphoric acid aqueous solution. The hydrogenated liquid at the outlet of the water washing unit can be kept neutral, and the acidity of the hydrogenated liquid at the outlet of the coalescer is 1-3 mg / L.

[0090] The wash water filtration unit contains two wash water filters, one in use and one as a backup. Each filter is equipped with eight filter cartridges (each measuring Φ80 x 1000mm). On average, all filter cartridges in one filter are replaced every two years when the pressure differential across the filter increases to ~100kPa. Removed filter cartridges are considered ordinary solid waste.

[0091] The hydrogenated liquid flowing out of the water washing unit is mixed with the acid liquid and directly enters the oxidation process without passing through the coalescer.

[0092] The oxidation process adopts a reaction extraction process that couples countercurrent oxidation and extraction.

[0093] The rest is the same as Example 1.

[0094] The oxidation yield is ~97%, there is no oxidation residue, and the extract stability is ~96%.

[0095] The hydrogenated liquid was taken from the hydrogenated liquid discharge pipe of the water washing unit and the metal ion content thereof was analyzed. The concentrations of palladium, iron, chromium, aluminum, potassium and sodium ions were all ≤10 μg / kg.

Claims

1. A hydrogenation liquid treatment device for producing hydrogen peroxide by an anthraquinone process, comprising a hydrogenation reaction unit (1), a hydrogenation liquid tank (2), a water washing unit (3), and a hydrogenation liquid pump (4) connected in sequence, wherein an acid liquid feeding port (14) is provided on the hydrogenation liquid discharge pipe of the water washing unit (3); and a washing water feeding pipe (9) is provided on the washing water feeding pipe (9), and a pure water feeding port (11) is provided on the washing water feeding pipe (9).

2. The hydrogenated liquid treatment device according to claim 1, characterized in that The hydrogenated liquid treatment device is provided with a washing water filter unit (6), the water washing unit (3) is provided with a washing water discharge pipe (8) connected to the washing water filter unit (6), and the washing water feed pipe (9) is connected to the washing water filter unit (6).

3. The hydrogenated liquid treatment device according to claim 1, characterized in that The hydrogenated liquid treatment device is provided with a washing water treatment unit (7), and the washing water filtering unit (6) is connected to the washing water treatment unit (7).

4. The hydrogenated liquid treatment device according to claim 3, characterized in that The washing water treatment unit (7) adopts one of chemical precipitation method, solvent extraction method, adsorption method, biological method and reverse osmosis method.

5. The hydrogenated liquid treatment device according to claim 1, wherein The hydrogenation reaction unit (1) is a fixed bed reaction unit or a gas-liquid-solid three-phase fluidized bed reaction unit.

6. The hydrogenated liquid treatment device according to claim 5, characterized in that The fixed bed reaction unit includes a fixed bed reactor and a gas-liquid separator connected to the fixed bed reactor, and the gas-liquid-solid three-phase fluidized bed reaction unit includes a gas-liquid-solid three-phase fluidized bed reactor and a primary filter connected to the gas-liquid-solid three-phase fluidized bed reactor.

7. The hydrogenated liquid treatment device according to claim 1, wherein The water washing unit (3) is selected from one of a stirred tank, a fiber membrane contactor, a sieve plate tower, a packed tower, and a static mixer.

8. The hydrogenated liquid treatment device according to claim 7, characterized in that The fiber membrane contactor refers to a contactor filled with curved fiber filaments, and the fiber filaments are hydrophilically treated; preferably, the fiber filaments are made of at least one of stainless steel, polytetrafluoroethylene, polypropylene, polyurethane, polyvinyl chloride, and polyester.

9. The hydrogenated liquid treatment device according to claim 1, characterized in that The hydrogenated liquid treatment device is provided with a coalescer (5), and the coalescer (5) is connected to the hydrogenated liquid pump (4).

10. The hydrogenated liquid treatment device according to claim 1, wherein A conductivity monitoring point (12) is provided on the washing water feed pipe (9) at a position after the washing water is mixed with the pure water supplied from the pure water feed port (11).

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