Process system and process method for preparing hydrogen peroxide by anthraquinone method
阅读说明：本技术 蒽醌法制取过氧化氢的工艺体系及工艺方法 (Process system and process method for preparing hydrogen peroxide by anthraquinone method ) 是由 傅骐 廖干昌 曹伦 郝晓斌 冯日洪 仪志宏 许平安 于 2021-07-26 设计创作，主要内容包括：本发明提供了一种蒽醌法制取过氧化氢的工艺体系及工艺方法,其工艺体系包括工作液和用于氧化工序及萃取工序的无磷助剂；其中无磷助剂为酒石酸、硝酸、柠檬酸、硼酸中的一种或几种,工作液包括溶剂和载体,溶剂为C-9～C-(10)的重芳烃(Ar)与2-甲基环己基醋酸酯的混合溶剂,或者C-9～C-(10)的重芳烃与四丁基脲(TBU)的混合溶剂,C-9～C-(10)的重芳烃与磷酸三辛酯(TOP)的混合溶剂,也可以是上述3种溶剂任意组合,还可以是C-9～C-(10)的重芳烃和二异丁基甲醇(DIBC)的混合溶剂；载体为2-乙基蒽醌或2-戊基蒽醌。本发明通过采用无磷助剂替代传统磷酸,不仅可以降低成本,还可以实现整个过氧化氢生产过程均处于无磷环境。(The invention provides a process system and a process method for preparing hydrogen peroxide by an anthraquinone method, wherein the process system comprises working solution and a phosphorus-free auxiliary agent used for an oxidation process and an extraction process; wherein the phosphorus-free auxiliary agent is one or more of tartaric acid, nitric acid, citric acid and boric acid, the working solution comprises solvent and carrier, and the solvent is C 9 ~C 10 A mixed solvent of the heavy aromatic hydrocarbon (Ar) and 2-methylcyclohexyl acetate, or C 9 ~C 10 A mixed solvent of a heavy aromatic hydrocarbon and tetrabutyl urea (TBU), C 9 ~C 10 The mixed solvent of heavy aromatic hydrocarbon and trioctyl phosphate (TOP) can be any combination of the 3 solvents, and can also be C 9 ~C 10 A mixed solvent of a heavy aromatic hydrocarbon and Diisobutylcarbinol (DIBC); the carrier is 2-ethyl anthraquinone or 2-amyl anthraquinone. The invention adopts the phosphorus-free auxiliary agent to replace the traditional phosphoric acid, thereby not only reducing the cost, but also realizing the whole hydrogen peroxide production process in a phosphorus-free environment.)
1. A process system for preparing hydrogen peroxide by an anthraquinone method is characterized in that: comprises working solution and non-phosphorus auxiliary agent used for oxidation process and extraction process; wherein the phosphorus-free auxiliary agent is one or more of tartaric acid, nitric acid, citric acid and boric acid.
2. The process system of claim 1, wherein: in the oxidation process, after the phosphorus-free auxiliary agent is added, the acidity of the oxidation liquid is 1-5 mg/L calculated by phosphoric acid; in the extraction process, after the phosphorus-free auxiliary agent is added, the acidity of the liquid is 0.1-0.5g/L calculated by phosphoric acid; the phosphorus-free auxiliary agent added in the oxidation procedure and the extraction procedure has the same components.
3. The process system of claim 1, wherein: in the phosphorus-free assistant, the content of tartaric acid is 0-5%, the content of citric acid is 0-5%, the content of nitric acid is 0-20%, the content of boric acid is 0-10%, and the balance is pure water.
4. The process system of claim 1, wherein: the working solution comprises a solvent and a carrier, wherein the solvent is a mixed solvent of C9-C10 heavy aromatic hydrocarbon and 2-methyl cyclohexyl acetate, or a mixed solvent of C9-C10 heavy aromatic hydrocarbon and tetrabutyl urea, or a mixed solvent of C9-C10 heavy aromatic hydrocarbon and trioctyl phosphate, or any combination of the 3 solvents, or a mixed solvent of C9-C10 heavy aromatic hydrocarbon and diisobutyl methanol; the carrier is 2-ethyl anthraquinone or 2-amyl anthraquinone.
5. The process system of claim 4, wherein: c in the solvent in a total volume percentage of 100%9~C10The proportion of heavy aromatics is 60-70%.
6. The process system according to any one of claims 1 to 5, characterized in that: the density of the working fluid is 910-3Viscosity of 1.20-1.60m2/s。
7. The process for producing hydrogen peroxide according to any one of claims 1 to 6, comprising the steps of:
s1, preparing a working solution, and allowing the working solution and hydrogen to enter a hydrogenation tower together to perform hydrogenation reaction at the active site of the catalyst to obtain a hydrogenation solution;
s2, adding the hydrogenated liquid into a phosphorus-free auxiliary agent, mixing, inputting into an oxidation tower, and carrying out oxidation reaction on the hydrogenated liquid and air to obtain an oxidation liquid;
s3, adding a phosphorus-free assistant and pure water into the oxidation liquid, mixing, and inputting the mixture into an extraction tower for extraction and separation to obtain a crude aqueous hydrogen peroxide solution;
and S4, inputting the crude hydrogen peroxide aqueous solution into a purification tower to extract with aromatic hydrocarbon, separating an organic phase, feeding the aqueous phase into a coalescence separator to further separate the organic phase, and blowing off the obtained aqueous phase by using compressed air to obtain a hydrogen peroxide product.
8. The process of claim 7, wherein: controlling the pressure to be 0.2-0.4MPa and the temperature to be 40-60 ℃ during the hydrogenation reaction in S1; during the oxidation reaction in S2, the pressure is controlled to be 0.2-0.4MPa and the temperature is controlled to be 45-55 ℃.
9. The process of claim 8, wherein: aromatic hydrocarbon used in the extraction in S3 and S4 is C9-C10 aromatic hydrocarbon, the extraction conditions are that the flow ratio of dispersed phase oxidation liquid and continuous phase pure water is 50-55: 1, and the extraction temperature is controlled at 45-55 ℃.
10. The process of claim 8, wherein: controlling the temperature of a coalescence separator in S4 to be 45-55 ℃; when the compressed air is blown off, the air flow rate is not lower than 5m/s, and the pore size of the open pore of the air distributor is not lower than 0.5 mm.
Technical Field
The invention relates to the field of fine chemical engineering, in particular to a process system and a process method for preparing hydrogen peroxide by an anthraquinone method.
Background
At present, most domestic hydrogen peroxide production devices adopt an anthraquinone method fixed bed process, 2-ethyl anthraquinone is used as a carrier, C9-C10 heavy aromatic hydrocarbon is used as a 2-ethyl anthraquinone solvent, one or two of trioctyl phosphate, acetic ester and tetrabutyl urea are used as a hydrogen anthraquinone solvent to form a working solution system, 2-amyl anthraquinone is used as a carrier abroad, C9-C10 heavy aromatic hydrocarbon and diisobutyl methanol are used as solvents to form a three-component working solution system, and finally, the working solution is subjected to hydrogenation, oxidation, extraction, purification and other processes to obtain a qualified hydrogen peroxide product.
In the hydrogen peroxide production process, the working solution contains trioctyl phosphate as a hydroanthraquinone solvent, which can be hydrolyzed under certain conditions to form organic phosphorus substances, and the process system uses phosphoric acid as an acidity regulator for oxidation and extraction processes, and the phosphorus substances often pass through a sewage and product outflow system in the system, so that the difficulty of sewage treatment and the quality of hydrogen peroxide products are greatly influenced.
Disclosure of Invention
The invention provides a process system and a process method for preparing hydrogen peroxide by an anthraquinone method, which can realize little phosphorus or no phosphorization and solve the problems that the treatment of phosphorus-containing sewage is difficult and the quality of downstream products is greatly influenced by the high content of phosphate of the products.
The technical scheme of the invention is that a process system for preparing hydrogen peroxide by an anthraquinone method comprises a working solution and a phosphorus-free auxiliary agent used for an oxidation process and an extraction process; wherein the phosphorus-free auxiliary agent is one or more of tartaric acid, nitric acid, citric acid and boric acid.
Further, in the oxidation process, after the phosphorus-free auxiliary agent is added, the acidity of the oxidation liquid is 1-5 mg/L; in the extraction process, after the phosphorus-free auxiliary agent is added, the acidity of the liquid is 0.1-0.5g/L calculated by phosphoric acid; the phosphorus-free auxiliary agent added in the oxidation procedure and the extraction procedure has the same components.
Furthermore, in the phosphorus-free assistant, the content of tartaric acid is 0-5%, the content of citric acid is 0-5%, the content of nitric acid is 0-20%, the content of boric acid is 0-10% and the balance is pure water by mass fraction. The phosphorus-free auxiliary agent can be a compound auxiliary agent of nitric acid and boric acid, can also be a compound auxiliary agent of tartaric acid and nitric acid, and can also be a compound auxiliary agent of tartaric acid, nitric acid, citric acid and boric acid, preferably the phosphorus-free auxiliary agent of tartaric acid, citric acid, nitric acid and boric acid is prepared according to the proportion of 1: 1: 5:2 mixed compound auxiliary agent.
Further, the working solution comprises a solvent and a carrier, wherein the solvent is a mixed solvent of a heavy aromatic hydrocarbon of C9-C10 and 2-methylcyclohexyl acetate, or a mixed solvent of a heavy aromatic hydrocarbon of C9-C10 and tetrabutyl urea, or a mixed solvent of a heavy aromatic hydrocarbon of C9-C10 and trioctyl phosphate, or any combination of the above 3 solvents, or a mixed solvent of a heavy aromatic hydrocarbon of C9-C10 and diisobutylcarbinol; the carrier is 2-ethyl anthraquinone or amyl anthraquinone.
Further, C is 100 percent of the total volume in the solvent9～C10The proportion of heavy aromatics is 60-70%.
Further, the density of the working solution is 910-3Viscosity of 1.20-1.60m2And s. Wherein when the carrier is 2-ethyl anthraquinone, the mass concentration of the 2-ethyl anthraquinone is 100-200 g/L; when the carrier is 2-amylanthraquinone, the mass concentration is 240-320 g/L.
The invention also relates to a process method for preparing hydrogen peroxide by the process system, which comprises the following steps:
s1, preparing a working solution, and allowing the working solution and hydrogen to enter a hydrogenation tower together to perform hydrogenation reaction at the active site of the catalyst to obtain a hydrogenation solution;
s2, adding the hydrogenated liquid into a phosphorus-free auxiliary agent, mixing, inputting into an oxidation tower, and carrying out oxidation reaction on the hydrogenated liquid and air to obtain an oxidation liquid;
s3, adding a phosphorus-free assistant and pure water into the oxidation liquid, mixing, and inputting the mixture into an extraction tower for extraction and separation to obtain a crude aqueous hydrogen peroxide solution;
and S4, inputting the crude hydrogen peroxide aqueous solution into a purification tower to extract with aromatic hydrocarbon, separating an organic phase, feeding the aqueous phase into a coalescence separator to further separate the organic phase, and blowing off the obtained aqueous phase by using compressed air to obtain a hydrogen peroxide product.
Further, the pressure is controlled to be 0.2-0.4MPa and the temperature is controlled to be 40-60 ℃ during the hydrogenation reaction in S1; during the oxidation reaction in S2, the pressure is controlled to be 0.2-0.4MPa and the temperature is controlled to be 45-55 ℃.
Further, the aromatic hydrocarbon used in the extraction in S3 and S4 is C9-C10 aromatic hydrocarbon, the extraction condition is that the flow ratio of the dispersed phase oxidation liquid to the continuous phase pure water is 50-55: 1, and the extraction temperature is controlled at 45-55 ℃;
further, the temperature of the coalescence separator in the S4 is controlled to be 45-55 ℃. When the compressed air is blown off, the air flow rate is not lower than 5m/s, and the pore size of the open pore of the air distributor is not lower than 0.5 mm.
The invention has the following beneficial effects:
1. the phosphate-free auxiliary agent is adopted to replace the traditional phosphoric acid auxiliary agent, so that the phosphate-free auxiliary agent has no great influence on the aspects of production process index control and product quality, can be widely applied to common working liquid systems at home and abroad as a substitute of phosphoric acid (mainly comprising a heavy aromatic hydrocarbon + trioctyl phosphate system, a heavy aromatic hydrocarbon + trioctyl phosphate + tetrabutyl urea system, a heavy aromatic hydrocarbon + trioctyl phosphate + 2-methylcyclohexyl acetate system, a heavy aromatic hydrocarbon + diisobutyl methanol system and the like), and has unit consumption cost of only about 50 percent of that of the traditional phosphoric acid. If single phosphorus-free inorganic acid is mostly strong acid, the acidity control of the inorganic acid is lack of buffer action, and the compound phosphorus-free auxiliary agent is preferably used as an acidic medium of hydrogen peroxide to replace phosphoric acid, so that the product quality can be ensured, and the acidic conditions of oxidation and extraction can also be ensured. For example, mixed acid of nitric acid and citric acid is selected as the phosphorus-free assistant.
2. In the phosphorus-free auxiliary agent, if organic acid is added, the organic acid is taken as an acidic substance, so that the content of organic carbon in a hydrogen peroxide product is increased, and the product quality is influenced.
3. For the existing process system and equipment for preparing hydrogen peroxide by anthraquinone method, the common working solution contains trioctyl phosphate, if the difficulty of replacing the phosphorus-free working solution is large, the original working solution is required to be completely returned and then supplemented with the phosphorus-free working solution, the operation has no operability from the cost aspect, and in order to reduce the phosphorus content in the product and the phosphorus content in the waste liquid, the problem can be solved by adding a phosphorus-free auxiliary agent. The phosphorus-containing working solution and the phosphorus-free auxiliary agent can reduce the phosphorus content, and in a more preferable scheme, the invention also provides the phosphorus-free working solution which adopts 2-ethylanthraquinone or 2-amylanthraquinone as a carrier and C9～C10The combination of the heavy aromatic hydrocarbon and the 2-methyl cyclohexyl acetate or the diisobutyl carbinol is used as a solvent to form a phosphorus-free working solution system, the solubility of the 2-ethyl anthraquinone in the system is 170-200g/L, the solubility of the 2-ethyl anthraquinone in unit volume is improved by about 20 percent, and the capacity of a hydrogen peroxide production device is improved. But the content of the 2-methyl cyclohexyl acetic ester in a phosphorus-free working solution system is relatively increased, so that the content of organic carbon in a later product is easily increased.
4. When the phosphorus-free working solution and the phosphorus-free auxiliary agent are adopted, the working solution system and the acidity regulation and control system do not contain phosphorus elements, so that the whole hydrogen peroxide production process is in a phosphorus-free environment, the problem of phosphorus treatment in sewage is solved, and the influence of high phosphate content on the quality of downstream products (such as caprolactam and propylene oxide) is reduced. Compared with the traditional working solution, the phosphorus-free working solution is favorable for reducing viscosity, can obviously improve extraction effect, can stably keep the extraction residue content below 0.15g/L, and meanwhile, the working solution has the advantages of 50-70% of the content of the oxidizing gas, shortened oxidizing retention time, improved oxidizing efficiency, reduced height of an oxidizing tower, reduced total amount of the circulating working solution of the system and reduced investment of the whole project.
Drawings
FIG. 1 is a process system for preparing hydrogen peroxide by anthraquinone process, which comprises a hydrogenation tower 1, a hydrogenation liquid pump 2, an oxidation tower 3, an extraction tower 4, a purification tower 5, a coalescing separator 6, a product stripping tank 7.
Detailed Description
Embodiments of the present invention will be described in detail below with reference to examples, but those skilled in the art will appreciate that the following examples are only illustrative of the present invention and should not be construed as limiting the scope of the present invention.
Part of experimental conditions are that the circulation flow of the working solution is 300L/h, and the hydrogen flow is 1.8m3The space velocity is 15 to 18 hours-1The pressure of the hydrogenation tower is 0.3MPa, the hydrogenation temperature is 55 ℃, the pressure of the oxidation tower is 0.35MPa, and the temperature of the oxidation tower is 55 ℃. The feasibility of replacing the traditional phosphoric acid by the acidic phosphorus-free auxiliary agent is verified by comparing the data of the acidic phosphorus-free auxiliary agent and the working solution system of the phosphoric acid for preparing hydrogen peroxide by the common anthraquinone method of heavy aromatic hydrocarbon + trioctyl phosphate, heavy aromatic hydrocarbon + 2-methylcyclohexyl acetate, heavy aromatic hydrocarbon + tetrabutyl urea, heavy aromatic hydrocarbon + trioctyl phosphate + 2-methylcyclohexyl acetate, and heavy aromatic hydrocarbon + diisobutyl carbinol.
Example 1
With C9～C10The heavy aromatic hydrocarbon and trioctyl phosphate are used as solvents, the volume ratio is 75:25, 2-ethyl anthraquinone is used as a carrier, a working solution system with the mass concentration of 130g/L is prepared, and the working solution and hydrogen gas enter a hydrogenation tower together to carry out hydrogenation reaction at an active site of a palladium catalyst (the content of Pd is 0.3 percent), so as to obtain hydrogenation solution. Pumping hydrogenated liquid into an oxidation tower through a delivery pump, respectively using phosphoric acid and acidic phosphorus-free auxiliary agents (1% of tartaric acid, 1% of citric acid, 5% of nitric acid, 2% of boric acid and the balance of pure water) as acidic substances to carry out a comparative experiment, controlling the acidity of the liquid before oxidation to be 5mg/L (calculated by phosphoric acid), carrying out oxidation reaction in the oxidation tower to obtain oxidation liquid, respectively adding the phosphoric acid and the acidic phosphorus-free auxiliary agents into the pure water, controlling the acidity of the pure water to be 0.3g/L (calculated by phosphoric acid), mixing and inputting the mixture into an extraction tower to carry out extraction separation to obtain crude hydrogen peroxide, inputting the crude hydrogen peroxide aqueous solution into a purification tower to carry out extraction with aromatic hydrocarbon at the temperature of 50-60 ℃, separating an organic phase, inputting the aqueous phase into a coalescence separator to further separate the organic phase, and using compressed air to obtain an aqueous phaseAnd blowing off to obtain a hydrogen peroxide product. Specific data are shown in table 1 below.
TABLE 1
Example 2
With C9～C10The heavy aromatic hydrocarbon and 2-methyl cyclohexyl acetate are used as solvents, the volume ratio is 65:35, 2-ethyl anthraquinone is used as a carrier, a phosphorus-free working solution system with the mass concentration of 170g/L is prepared, and the phosphorus-free working solution and hydrogen enter a hydrogenation tower together to carry out hydrogenation reaction at an active site of a palladium catalyst (the content of Pd is 0.3 percent), so that hydrogenated liquid is obtained. Pumping the hydrogenated liquid into an oxidation tower through a delivery pump, respectively adding an acidic phosphorus-free auxiliary agent (1% of tartaric acid, 1% of citric acid, 5% of nitric acid, 2% of boric acid and the balance of pure water) and phosphoric acid in front of the pump to perform a comparative experiment, controlling the acidity of the liquid before oxidation to be 5mg/L (calculated by phosphoric acid), performing an oxidation reaction in the oxidation tower to obtain hydrogen peroxide, respectively adding phosphoric acid and the acidic phosphorus-free auxiliary agent into the pure water, controlling the acidity of the pure water to be 0.2g/L (calculated by phosphoric acid), mixing, and inputting the mixed liquid into an extraction tower for extraction and separation to obtain crude hydrogen peroxide; inputting the crude aqueous hydrogen peroxide solution into a purification tower, extracting with aromatic hydrocarbon at the temperature of 50-60 ℃, separating an organic phase, feeding an aqueous phase into a coalescence separator for further separating the organic phase, and blowing off the obtained aqueous phase by utilizing compressed air to obtain the hydrogen peroxide solution, wherein specific data are shown in table 2 below.
TABLE 2
It can be clearly seen from table 2 that the substitution of the acidic phosphorus-free auxiliary agent for the traditional phosphoric acid does not cause a great influence on the heavy aromatic hydrocarbon + acetic ester working solution system, the phosphorus content in the final product is not detected due to the introduction of phosphorus, the product quality is greatly improved, and the quality of organic carbon in the product under the working solution system can be better ensured due to the technical scheme of aromatic hydrocarbon purification, coalescence separation and gas stripping.
Example 3:
with C9～C10The method comprises the steps of taking heavy aromatic hydrocarbon and tetrabutyl urea as solvents in a volume ratio of 70:30, taking 2-ethylanthraquinone as a carrier, preparing a working solution system with a mass concentration of 150g/L, feeding the working solution and hydrogen into a hydrogenation tower together, carrying out hydrogenation reaction on an active site with a palladium catalyst (the content of Pd is 0.3 percent) to obtain a hydrogenated liquid, pumping the hydrogenated liquid into an oxidation tower through a delivery pump, respectively using a phosphoric acid solution with a mass fraction of 50 percent and an acidic non-phosphorus auxiliary agent (1 percent of tartaric acid, 1 percent of citric acid, 5 percent of nitric acid, 2 percent of boric acid and the balance of pure water) as acidic substances to carry out a comparison experiment, controlling the acidity of the hydrogenated liquid to be 5mg/L (measured by phosphoric acid), carrying out oxidation reaction in the oxidation tower to obtain an oxidized liquid, respectively adding phosphoric acid and the acidic non-phosphorus auxiliary agent into the pure water, mixing, feeding the oxidized liquid and the mixed liquid into an extraction tower for extraction and separation, crude hydrogen peroxide is obtained. Inputting the crude aqueous hydrogen peroxide solution into a purification tower, extracting with aromatic hydrocarbon at the temperature of 50-60 ℃, separating an organic phase, feeding an aqueous phase into a coalescence separator for further separating the organic phase, and blowing off the obtained aqueous phase by utilizing compressed air to obtain the hydrogen peroxide solution, wherein specific data are shown in Table 3 below.
TABLE 3
As can be seen from Table 3, the use of the acidic phosphorus-free auxiliary agent instead of the conventional phosphoric acid does not cause a great influence on the working solution system of heavy aromatic hydrocarbon and tetrabutyl urea, and the phosphorus content in the final product is not detected due to the absence of the introduction of phosphorus,
example 4
With C9～C10The heavy aromatic hydrocarbon, trioctyl phosphate and 2-methyl cyclohexyl acetate are used as solvents, the volume ratio is 75:10:15, and 2-ethyl anthracene is usedQuinone is used as a carrier, a working solution system with the mass concentration of 150g/L is prepared, and the working solution and hydrogen enter a hydrogenation tower together to carry out hydrogenation reaction at an active site of a palladium catalyst (the Pd content is 0.3%) to obtain a hydrogenation solution. The hydrogenated liquid is pumped into an oxidation tower through a delivery pump, phosphoric acid and a phosphorus-free auxiliary agent (the components are the same as in example 1) are respectively used as acidic substances to carry out a comparative experiment, oxidation reaction is carried out in the oxidation tower to obtain hydrogen peroxide oxidized liquid, then phosphoric acid and the acidic phosphorus-free auxiliary agent (the components are the same as in example 1) are respectively added into pure water, the acidity of the pure water is controlled to be 0.3g/L (calculated by phosphoric acid), the mixture is input into an extraction tower to carry out extraction separation, and crude hydrogen peroxide is obtained. Inputting the crude aqueous hydrogen peroxide solution into a purification tower, extracting with aromatic hydrocarbon at the temperature of 50-60 ℃, separating an organic phase, feeding an aqueous phase into a coalescence separator for further separating the organic phase, and blowing off the obtained aqueous phase by utilizing compressed air to obtain the hydrogen peroxide solution, wherein specific data are shown in Table 4 below.
TABLE 4
As is clear from table 4, the acidic phosphorus-free assistant used in place of the conventional phosphoric acid has no significant effect on the working solution system of heavy aromatic hydrocarbon, trioctyl phosphate and 2-methylcyclohexyl acetate, and the phosphorus content in the final product is only the hydrolysis and entrainment content of trioctyl phosphate due to no introduction of phosphorus, and is much lower than that of the conventional phosphoric acid.
Example 5
With C9～C10The heavy aromatic hydrocarbon, trioctyl phosphate and tetrabutyl urea are used as solvents, the volume ratio is 75:10:15, 2-ethyl anthraquinone is used as a carrier, a working solution system with the mass concentration of 150g/L is prepared, and the working solution and hydrogen gas enter a hydrogenation tower together to carry out hydrogenation reaction at an active site of a palladium catalyst (the content of Pd is 0.3 percent), so as to obtain a hydrogenation solution. The hydrogenated liquid is pumped into an oxidation tower by a delivery pump, phosphoric acid and an acidic phosphorus-free auxiliary agent (the components are the same as in example 1) are respectively used as acidic substances to carry out a comparative experiment, oxidation reaction is carried out in the oxidation tower to obtain oxidation liquid, and then the oxidation liquid is respectively added into pure waterPhosphoric acid and the above acidic phosphorus-free assistant (the same components as in example 1) were added, and the acidity of purified water was controlled to 0.4g/L (in terms of phosphoric acid), and the mixture was fed into an extraction column to be extracted and separated, thereby obtaining crude hydrogen peroxide. Inputting the crude hydrogen peroxide aqueous solution into a purification tower, extracting with aromatic hydrocarbon at 50-60 ℃, separating an organic phase, feeding an aqueous phase into a coalescence separator for further separating the organic phase, and blowing off the obtained aqueous phase by using compressed air to obtain a hydrogen peroxide product, wherein specific data are shown in Table 5.
TABLE 5
As is clear from table 5, the acidic phosphorus-free adjuvant used in place of the conventional phosphoric acid does not have a great influence on the working solution system of heavy aromatic hydrocarbon, trioctyl phosphate and tetrabutyl urea, and the phosphorus content in the final product is only the content of trioctyl phosphate hydrolysis and entrainment, and is far lower than that of the conventional phosphoric acid due to the absence of the adjuvant phosphorus.
Example 6:
with C9～C10The heavy aromatic hydrocarbon and diisobutyl carbinol are used as solvents, the volume ratio is 70:30, 2-amylanthraquinone is used as a carrier, a working solution system with the mass concentration of 300g/L is prepared, and the working solution and hydrogen enter a hydrogenation tower together to carry out hydrogenation reaction at the active site of a palladium catalyst (the content of Pd is 0.3 percent), so as to obtain hydrogenation solution. The hydrogenated liquid is pumped into an oxidation tower through a delivery pump, phosphoric acid and an acidic phosphorus-free auxiliary agent (the components are the same as in example 1) are respectively used as acidic substances to carry out a comparative experiment, oxidation reaction is carried out in the oxidation tower to obtain an oxidation liquid, then the phosphoric acid and the acidic phosphorus-free auxiliary agent (the components are the same as in example 1) are respectively added into the oxidation liquid to be mixed, and the mixture is input into an extraction tower to be extracted and separated, so that crude hydrogen peroxide is obtained. Inputting the crude aqueous hydrogen peroxide solution into a purification tower, extracting with aromatic hydrocarbon at the temperature of 50-60 ℃, separating an organic phase, feeding an aqueous phase into a coalescence separator for further separating the organic phase, and blowing off the obtained aqueous phase by utilizing compressed air to obtain the hydrogen peroxide solution, wherein specific data are shown in Table 6 below.
TABLE 6
It is clear from table 6 that the substitution of the conventional phosphoric acid with the acidic phosphorus-free adjuvant did not cause any significant effect on the pentylanthraquinone working fluid system of heavy aromatics + diisobutylcarbinol, and the phosphorus content in the final product was not detected due to the absence of the introduction of phosphorus.
Example 7:
with C9～C10The heavy aromatic hydrocarbon and 2-methyl cyclohexyl acetate are used as solvents, the volume ratio is 65:35, 2-ethyl anthraquinone is used as a carrier, a phosphorus-free working solution system with the mass concentration of 170g/L is prepared, and the phosphorus-free working solution and hydrogen enter a hydrogenation tower together to carry out hydrogenation reaction at an active site of a palladium catalyst (the content of Pd is 0.3 percent), so that hydrogenated liquid is obtained. Pumping the hydrogenated liquid into an oxidation tower through a delivery pump, respectively adding phosphoric acid, a phosphorus-free auxiliary agent 1 (nitric acid 5%), a phosphorus-free auxiliary agent 2 (nitric acid 5%, tartaric acid 1% and citric acid 1%) and a phosphorus-free auxiliary agent 3 (boric acid 5% and tartaric acid 1%) in front of the pump to perform a comparison experiment, controlling the acidity of the liquid before oxidation to be 5mg/L (calculated by phosphoric acid), performing an oxidation reaction in the oxidation tower to obtain hydrogen peroxide, respectively adding phosphoric acid and the phosphorus-free acidic auxiliary agent into pure water, controlling the acidity of the pure water to be 0.2g/L (calculated by phosphoric acid), mixing, inputting the mixed water into an extraction tower, and performing extraction separation to obtain crude hydrogen peroxide; inputting the crude aqueous hydrogen peroxide solution into a purification tower, extracting with aromatic hydrocarbon at the temperature of 50-60 ℃, separating an organic phase, feeding an aqueous phase into a coalescence separator for further separating the organic phase, and blowing off the obtained aqueous phase by utilizing compressed air to obtain the hydrogen peroxide solution, wherein specific data are shown in Table 7 below.
TABLE 7
The phosphorus-free working solution system and the phosphorus-free auxiliary agent can well achieve the phosphorus-free effect, and almost have no great influence on other quality indexes of the product. And for some existing devices, an acidic phosphorus-free auxiliary agent can be selected to replace the traditional phosphoric acid, so that the phosphorus content of the product and the wastewater can be greatly reduced, and the product quality and the difficulty degree of wastewater treatment are greatly improved.