Comprehensive utilization device of nitric acid containing organic matters

Abstract

The utility model provides a comprehensive utilization device for nitric acid containing organic matters, which is characterized in that the nitric acid containing organic matters generated by nitration reaction of substituted benzoic acid and nitric acid in a nitric acid containing organic matters generation unit is directly added into a neutralization reaction kettle and is subjected to neutralization reaction with alkaline substances added into the neutralization reaction kettle to obtain a neutralization solution containing nitrate and organic matters; solid-phase organic matters and a liquid-phase nitrate solution are separated through the first solid-liquid separator, so that a nitrate product can be obtained, the organic matters can be efficiently recycled, the utilization rate of nitric acid is increased, and the production cost is reduced; the separated solid-phase organic matter enters the organic matter purification and separation unit to be purified and separated, so that the purity of the recycled organic matter is improved.

Description

Technical Field

[0001] The utility model belongs to the technical field of chemical equipment, and in particular relates to a comprehensive utilization device containing organic nitric acid. Background Art

[0002] When nitrating benzoic acid containing electron-donating groups, only nitric acid can be used as the nitrating agent. However, excessive nitric acid is generally used, which will produce a large amount of organic nitric acid. Direct discharge will seriously endanger the environment and human health. According to national policies and relevant laws, organic nitric acid must be strictly treated to meet emission standards before it can be discharged, and the treatment cost is relatively high. With the increasingly fierce competition in the industry, companies are paying more and more attention to the recycling and utilization of resources. In recent years, the concentration treatment of organic nitric acid has become a hot research topic. Before concentrating organic nitric acid, it is necessary to remove the organic matter dissolved in the nitric acid by dilution separation or extraction. Otherwise, the organic matter accumulated during the concentration process will undergo side reactions such as decomposition when heated for a long time, posing a major safety hazard. In addition, the concentration treatment requires high equipment investment and operating costs.

[0003] Although the prior art has already used waste nitric acid generated in the inorganic industry for liquid fertilizers such as ammonium nitrate, calcium magnesium, etc., such as patent CN210457985U, which combines waste nitric acid generated in the electroplating industry with substances containing calcium and magnesium in a secondary reaction tank to prepare ammonium nitrate, calcium magnesium fertilizer, no technology has been developed for the direct comprehensive utilization of organic nitric acid containing organic substances in the organic industry other than concentration treatment. Utility Model Content

[0004] The purpose of the utility model is to provide a comprehensive utilization device containing organic nitric acid. The comprehensive utilization device in the utility model has simple process, high nitric acid utilization rate and is green and environmentally friendly.

[0005] The utility model provides a comprehensive utilization device of organic nitric acid, comprising an organic nitric acid generating unit, a neutralization reactor, a first solid-liquid separator and an organic purification and separation unit;

[0006] The organic nitric acid outlet of the organic nitric acid generating unit is connected to the organic nitric acid inlet of the neutralization reactor, the outlet of the neutralization reactor is connected to the inlet of the first solid-liquid separator, the liquid phase outlet of the first solid-liquid separator is connected to the inlet of the nitrate solution collection tank; the solid phase outlet of the first solid-liquid separator is connected to the inlet of the organic matter purification and separation unit;

[0007] The neutralization reactor is also provided with an alkaline substance inlet.

[0008] Preferably, the organic matter purification and separation unit comprises a alkali adjustment kettle, a second solid-liquid separator and an acidification separation unit connected in sequence;

[0009] The acidification and separation unit includes at least one primary acidification and separation subunit; the acidification and separation subunit includes an acidification kettle and an acidification liquid-solid-liquid separator connected in sequence;

[0010] The outlet of the alkali adjustment kettle is connected to the acidification kettle, and the alkali adjustment kettle is also provided with an alkali solution inlet;

[0011] The acidification kettle is also provided with an acid liquid inlet.

[0012] Preferably, the neutralization reactor is also provided with a water inlet.

[0013] Preferably, the organic-containing nitric acid production unit comprises a nitration reaction unit and a third solid-liquid separator connected in sequence;

[0014] The liquid phase outlet of the third solid-liquid separator is communicated with the organic nitric acid inlet of the neutralization reactor.

[0015] Preferably, the organic-containing nitric acid production unit further comprises a dilution unit and a fourth solid-liquid separator connected in sequence;

[0016] The liquid phase outlet of the third solid-liquid separator is connected to the inlet of the dilution unit, the outlet of the dilution unit is connected to the inlet of the fourth solid-liquid separator, and the liquid phase outlet of the fourth solid-liquid separator is connected to the organic nitric acid inlet of the neutralization reactor.

[0017] Preferably, the nitration reaction unit comprises at least one primary reactor, and the reactor comprises a tubular reactor, a tank reactor, or a tubular reactor and a tank reactor connected in series.

[0018] Preferably, the comprehensive utilization device further comprises a nitrate separation unit;

[0019] The inlet of the nitrate separation unit is communicated with the outlet of the nitrate solution collecting tank.

[0020] Preferably, the nitrate separation unit comprises a concentration unit, a material transfer pump and a granulation unit which are connected in sequence;

[0021] The inlet of the concentration unit is communicated with the outlet of the nitrate solution collecting tank.

[0022] Preferably, the concentration unit comprises a preheater and a separation device connected in series, the separation device is at least a single-effect separator; the separator comprises a heater and a separation chamber connected in series.

[0023] Preferably, the comprehensive utilization device further comprises an adsorption unit;

[0024] The liquid phase outlet of the first solid-liquid separator is connected to the feed port of the adsorption unit, and the discharge port of the adsorption unit is connected to the inlet of the nitrate solution collection tank. The utility model provides a comprehensive utilization device for organic nitric acid, wherein the organic nitric acid produced by the nitration reaction of substituted benzoic acid and nitric acid in the organic nitric acid production unit is directly added to a neutralization reactor, and a neutralization reaction occurs with the alkaline substance added to the neutralization reactor to obtain a neutralized liquid containing nitrate and organic matter, and then the solid phase organic matter and the liquid phase nitrate solution are separated by the first solid-liquid separator, thereby not only obtaining a nitrate product, but also efficiently recovering the organic matter, improving the utilization rate of nitric acid and reducing production costs; the separated solid phase organic matter enters the organic matter purification and separation unit, and the purity of the recovered organic matter is improved after purification and separation.

[0025] Furthermore, the establishment of the alkali adjustment kettle, the second solid-liquid separator and at least one stage of acidification and separation unit not only further improves the purity of the recovered organic matter, but also avoids the loss of organic matter during the purification and separation process, realizes the recovery of high-purity organic matter with high yield, and further realizes the utilization value of organic-containing nitric acid.

[0026] Furthermore, the provision of a dilution unit in the organic-containing nitric acid production unit or the provision of a water inlet on the neutralization reactor can allow the nitrate generated by the reaction to be fully dissolved in the aqueous solution, while allowing the organic matter in the organic-containing nitric acid to be fully precipitated, thereby ensuring that the nitrate generated by the reaction and the organic matter can be fully separated and also improving the flexibility of the device. BRIEF DESCRIPTION OF THE DRAWINGS

[0027] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are merely embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on the provided drawings without paying any creative work.

[0028] Figure 1 This is a schematic structural diagram of the device used in Example 1 of the present utility model;

[0029] Figure 2 This is a schematic structural diagram of the device used in Example 2 of the present utility model;

[0030] Figure 3 This is a schematic structural diagram of the device used in Example 3 of the present utility model;

[0031] Figure 4 This is a schematic structural diagram of the device used in Example 4 of the present utility model;

[0032] Figure 5This is a schematic diagram of the structure of the device used in Example 5 of the present utility model;

[0033] Figure 6 This is a schematic structural diagram of the nitrate separation unit 7 used in Example 1 of the present utility model.

[0034] Among them, it contains an organic nitric acid production unit 1, a neutralization reactor 2, a first solid-liquid separator 3, a nitrate solution collection tank 4, an organic matter purification and separation unit 5, an acidification separation unit 6, a nitrate separation unit 7, an adsorption unit 8, a nitration reaction unit 1-1, a third solid-liquid separator 1-2, a dilution unit 1-3, a fourth solid-liquid separator 1-4, an alkali adjustment kettle 5-1, a second solid-liquid separator 5-2, a first acidification kettle 6-1, a first acidified liquid-solid-liquid separator 6-2, a second acidification kettle 6-3, a second acidified liquid-solid-liquid separator 6-4, a third acidification kettle 6-5, a third acidified liquid-solid-liquid separator 6-6, a concentration unit 7-1, a material transfer pump 7-2, a granulation unit 7-3, a preheater 7-1-1, a three-effect separator 7-1-2, a first heater a, a first separation chamber b, a second heater c, a second separation chamber d, a third heater e, and a third separation chamber f. DETAILED DESCRIPTION

[0035] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0036] The utility model provides a comprehensive utilization device containing organic nitric acid, comprising an organic nitric acid generating unit 1, a neutralization reaction kettle 2, a first solid-liquid separator 3 and an organic purification and separation unit 5;

[0037] The organic nitric acid outlet of the organic nitric acid generating unit 1 is connected to the organic nitric acid inlet of the neutralization reactor 2, the outlet of the neutralization reactor 2 is connected to the inlet of the first solid-liquid separator 3, the liquid phase outlet of the first solid-liquid separator 3 is connected to the inlet of the nitrate solution collecting tank 4; the solid phase outlet of the first solid-liquid separator 3 is connected to the inlet of the organic purification and separation unit 5;

[0038] The neutralization reactor 2 is also provided with an alkaline substance inlet.

[0039] The device provided by the utility model is used for the comprehensive utilization of organic nitric acid. It directly reacts the organic nitric acid with an alkaline substance to synthesize nitrates while separating and recovering the organic matter in the organic nitric acid. The organic matter is the mononitration product of a substituted benzoic acid and nitric acid, referred to as a mononitrated substituted benzoic acid. The substituted benzoic acid is a benzoic acid substituted with any electron-donating group, preferably one of o-methylbenzoic acid, m-methylbenzoic acid, and p-methylbenzoic acid. The alkaline substance is a metal hydroxide, a metal oxide, a carbonate, or a bicarbonate, preferably one or more of sodium bicarbonate, calcium carbonate, magnesium carbonate, calcium oxide, calcium hydroxide, and magnesium oxide.

[0040] Organic nitric acid and an alkaline substance are added to a neutralization reactor 2 for a neutralization reaction. The nitrate generated during the reaction is completely dissolved in the aqueous solution. As the reaction proceeds, the nitric acid concentration gradually decreases, and the organic matter originally dissolved in the nitric acid precipitates, resulting in a neutralized solution containing nitrate and organic matter. The neutralized solution is then fed to a first solid-liquid separator 3 for solid-liquid separation, yielding a first solid-phase organic matter and a first liquid-phase nitrate aqueous solution. This device not only produces an aqueous nitrate solution but also separates the organic matter from the organic nitric acid. The first solid-phase organic matter separated by the first solid-liquid separator 3 is fed to an organic matter purification and separation unit 5 for further separation and removal of impurities from the organic matter, thereby improving the utilization rate of the nitric acid and recovering high-quality organic matter.

[0041] In one embodiment of the present invention, the organic matter purification and separation unit 5 includes a alkali adjustment kettle 5-1, a second solid-liquid separator 5-2 and an acidification separation unit 6 which are connected in sequence;

[0042] The solid phase outlet of the first solid-liquid separator 3 is connected to the feed port of the alkali adjustment kettle 5-1 in the organic matter purification and separation unit 5. The first solid phase organic matter separated from the first solid-liquid separator 3 enters the alkali adjustment kettle 5-1 and reacts with the alkali solution added to the alkali adjustment kettle 5-1. As the reaction proceeds, the mononitrated substituted benzoic acid is converted into a mononitrated substituted benzoate and dissolved in the aqueous solution. The resulting reaction liquid flows out of the outlet of the alkali adjustment kettle 5-1 and enters the second solid-liquid separator 5-2 for solid-liquid separation to remove solid phase impurities introduced by the alkaline substance to obtain a second liquid phase. The second liquid phase flowing out of the liquid phase outlet of the second solid-liquid separator 5-2 enters the acidification and separation unit 6, which is composed of at least one stage of acidification kettle and solid-liquid separator connected in series, for acidification and separation. During the acidification process, the mononitrated substituted benzoate is converted into mononitrated substituted benzoic acid and precipitated in solid form. The purified organic matter can then be obtained through solid-liquid separation. Optional alkali solutions include sodium hydroxide solution, sodium bicarbonate solution, and sodium carbonate solution. Optional acids include sulfuric acid, hydrochloric acid, and nitric acid.

[0043] To fully recover the organic matter dissolved in the organic-containing nitric acid and improve the recovery rate of the organic matter, the neutralization reactor 2 in the apparatus provided by the present invention is further provided with a water inlet. Water enters the neutralization reactor 2 through the water inlet to dilute the reaction system of the organic-containing nitric acid and the alkaline substance, thereby more fully dissolving the nitrates generated by the reaction and allowing the organic matter in the organic-containing nitric acid to be fully precipitated. The addition of water also allows the neutralization reaction to proceed more fully.

[0044] In one embodiment of the present invention, the acidification and separation unit 6 includes at least one stage of acidification and separation subunit; the acidification and separation subunit includes an acidification kettle and an acidification liquid-solid-liquid separator that are connected in sequence.

[0045] In one embodiment of the present invention, the acidification and separation unit 6 includes a primary acidification and separation subunit, which includes a first acidification kettle 6-1 and a first acidification liquid-solid-liquid separator 6-2 connected in sequence, the liquid phase outlet of the second solid-liquid separator 5-2 is connected to the inlet of the first acidification kettle 6-1, and the outlet of the first acidification kettle 6-1 is connected to the inlet of the first acidification liquid-solid-liquid separator 6-2, and solid-phase organic matter is obtained from the solid phase outlet of the first acidification liquid-solid-liquid separator 6-2.

[0046] In one embodiment of the present invention, the acidification and separation unit 6 includes two-stage acidification and separation subunits, namely a first acidification and separation subunit and a second acidification and separation subunit connected in sequence. The first acidification and separation subunit includes a first acidification kettle 6-1 and a first acidification liquid-solid-liquid separator 6-2 connected in sequence, the liquid phase outlet of the second solid-liquid separator 5-2 is connected to the inlet of the first acidification kettle 6-1, and the outlet of the first acidification kettle 6-1 is connected to the inlet of the first acidification liquid-solid-liquid separator 6-2; the second acidification and separation subunit includes a second acidification kettle 6-3 and a second acidification liquid-solid-liquid separator 6-4 connected in sequence, the liquid phase outlet of the first acidification liquid-solid-liquid separator 6-2 is connected to the inlet of the second acidification kettle 6-3, and the outlet of the second acidification kettle 6-3 is connected to the inlet of the second acidification liquid-solid-liquid separator 6-4, and the solid-phase organic matter is obtained from the solid phase outlet of the second acidification liquid-solid-liquid separator 6-4.

[0047] In one embodiment of the present invention, the acidification and separation unit 6 includes three-stage acidification and separation subunits, namely, a first acidification and separation subunit, a second acidification and separation subunit and a third acidification and separation subunit connected in sequence, the first acidification and separation subunit includes a first acidification kettle 6-1 and a first acidification liquid-solid-liquid separator 6-2 connected in sequence, the liquid phase outlet of the second solid-liquid separator 5-2 is connected to the inlet of the first acidification kettle 6-1, and the outlet of the first acidification kettle 6-1 is connected to the inlet of the first acidification liquid-solid-liquid separator 6-2; the second acidification and separation subunit includes a second acidification kettle 6-3 and a second acidification liquid The solid-liquid separator 6-4, the liquid phase outlet of the first acidified liquid-solid-liquid separator 6-2 is connected to the inlet of the second acidified kettle 6-3, and the outlet of the second acidified kettle 6-3 is connected to the inlet of the second acidified liquid-solid-liquid separator 6-4; the third acidification and separation subunit includes a third acidified kettle 6-5 and a third acidified liquid-solid-liquid separator 6-6 connected in sequence, the liquid phase outlet of the second acidified liquid-solid-liquid separator 6-4 is connected to the inlet of the third acidified kettle 6-5, and the outlet of the third acidified kettle 6-5 is connected to the inlet of the third acidified liquid-solid-liquid separator 6-6, and the solid-phase organic matter is obtained from the solid phase outlet of the third acidified liquid-solid-liquid separator 6-6.

[0048] In one embodiment of the present invention, the organic-containing nitric acid production unit 1 includes a nitration reaction unit 1-1 and a third solid-liquid separator 1-2 connected in sequence, and the liquid phase outlet of the third solid-liquid separator 1-2 is connected to the organic-containing nitric acid inlet of the neutralization reactor 2.

[0049] In the present invention, substituted benzoic acid and excess nitric acid enter the nitration reaction unit 1-1 to undergo a nitration reaction to obtain a nitration reaction liquid containing mononitrated substituted benzoic acid and nitric acid. The nitration reaction liquid enters the third solid-liquid separator 1-2 to separate the third solid phase mononitrated substituted benzoic acid and the third liquid phase containing organic nitric acid. The organic nitric acid is directly added to the neutralization reactor 2 to undergo a neutralization reaction with the alkaline substance.

[0050] In another embodiment of the present invention, the organic-containing nitric acid production unit 1 further includes a dilution unit 1-3 and a fourth solid-liquid separator 1-4 connected in sequence, the liquid phase outlet of the third solid-liquid separator 1-2 is connected to the inlet of the dilution unit 1-3, the outlet of the dilution unit 1-3 is connected to the inlet of the fourth solid-liquid separator 1-4, and the liquid phase outlet of the fourth solid-liquid separator 1-4 is connected to the organic-containing nitric acid inlet of the neutralization reactor 2.

[0051] Substituted benzoic acid and excess nitric acid enter the nitration reaction unit 1-1 for a nitration reaction, producing a nitration reaction liquid containing mononitrated substituted benzoic acid and nitric acid. The nitration reaction liquid then enters the third solid-liquid separator 1-2 to separate the third solid phase of mononitrated substituted benzoic acid from the third liquid phase. The third liquid phase enters the dilution kettle of the dilution unit 1-3, where it is diluted with water, causing partial precipitation of the mononitrated substituted benzoic acid. The diluted liquid then enters the fourth solid-liquid separator 1-4 to separate the fourth solid phase of mononitrated substituted benzoic acid from the fourth liquid phase containing organic nitric acid. The organic nitric acid is then directly added to the neutralization reactor 2 for a neutralization reaction with an alkaline substance. The establishment of the dilution unit 1-3 reduces the concentration of the organic nitric acid and the content of organic matter therein, thereby avoiding or reducing the amount of water used during the neutralization reaction.

[0052] The organic nitric acid from the organic nitric acid generating unit 1 is directly added to the neutralization reactor 2 to undergo a neutralization reaction with the alkaline substance, thereby omitting the pretreatment of the organic nitric acid, improving the utilization rate of the nitric acid, and reducing the production cost.

[0053] In one embodiment of the present invention, the nitration reaction unit 1-1 includes at least one primary reactor, and the reactor includes a tubular reactor, a tank reactor, or a tubular reactor and a tank reactor connected in series.

[0054] To obtain a solid nitrate product, as a preferred technical solution, the apparatus further comprises a nitrate separation unit 7 connected to the nitrate solution collection tank 4. The nitrate separation unit 7 comprises a concentration unit 7-1, a transfer pump 7-2, and a granulation unit 7-3. The discharge port of the concentration unit 7-1 is connected to the feed port of the granulation unit 7-3 via the transfer pump 7-2.

[0055] In one embodiment of the present invention, the concentrating unit 7-1 is provided with a preheater 7-1-1 and a separator connected in series. The separator includes at least one single-effect separator, wherein the separator is a heater and a separation chamber connected to each other. To save energy, the concentrating unit 7-1 is preferably provided with a preheater 7-1-1 and a second-effect separator connected in series, or a preheater 7-1-1 and a third-effect separator 7-1-2 connected in series.

[0056] In one embodiment of the present invention, the concentration unit 7-1 is a preheater 7-1-1 and a single-effect separator connected in series, and the single-effect separator includes a first heater a and a first separation chamber b connected in sequence, the outlet of the preheater 7-1-1 is connected to the inlet of the first heater a, the outlet of the first heater a is connected to the inlet of the first separation chamber b, and the concentrated liquid outlet of the first separation chamber b is respectively connected to the inlet of the first heater a and the inlet of the granulation unit 7-3.

[0057] In one embodiment of the present invention, the concentration unit 7-1 is a preheater 7-1-1 and a two-effect separator connected in series in sequence, and the two-effect separator includes a first heater a, a first separation chamber b, a second heater c and a second separation chamber d connected in sequence, the outlet of the preheater 7-1-1 is connected to the inlet of the first heater a, the outlet of the first heater a is connected to the inlet of the first separation chamber b, the concentrated liquid outlet of the first separation chamber b is respectively connected to the inlet of the first heater a and the inlet of the second heater c, the outlet of the second heater c is connected to the inlet of the second separation chamber d, and the concentrated liquid outlet of the second separation chamber d is respectively connected to the inlet of the second heater c and the inlet of the granulation unit 7-3.

[0058] In one embodiment of the present invention, the concentration unit 7-1 is a preheater 7-1-1 and a triple-effect separator 7-1-2 connected in series in sequence, and the triple-effect separator 7-1-2 includes a first heater a, a first separation chamber b, a second heater c, a second separation chamber d, a third heater e and a third separation chamber f connected in sequence, the outlet of the preheater 7-1-1 is connected to the inlet of the first heater a, the outlet of the first heater a is connected to the inlet of the first separation chamber b, the concentrated liquid outlet of the first separation chamber b is respectively connected to the inlet of the first heater a and the inlet of the second heater c, the outlet of the second heater c is connected to the inlet of the second separation chamber d, the concentrated liquid outlet of the second separation chamber d is respectively connected to the inlet of the second heater c and the inlet of the third heater e, the outlet of the third heater e is connected to the inlet of the third separation chamber f, and the concentrated liquid outlet of the third separation chamber f is respectively connected to the inlet of the third heater e and the inlet of the granulation unit 7-3.

[0059] In order to facilitate the storage, transportation and use of solid nitrate, as a preferred technical solution, the granulation unit 7-3 uses a drum fluidized bed, and the discharge port of the concentration unit 7-1 is connected to the feed port of the drum fluidized bed through a transfer pump 7-2.

[0060] The nitrate solution collected in the nitrate solution collection tank 4 is heated by the preheater 7-1-1 and then enters at least one effective separator for concentration. The concentrated liquid is transported to the drum fluidized bed granulation unit 7-3 for granulation via the transfer pump 7-2. The granulated solid is screened, and the qualified nitrate is collected and packaged. The unqualified nitrate is cooled and returned to the drum fluidized bed granulation unit 7-3 for further granulation.

[0061] In order to improve the purity of the nitrate solution, in one embodiment of the present invention, the comprehensive utilization device containing organic nitric acid further includes an adsorption unit 8, the liquid phase outlet of the first solid-liquid separator 3 is connected to the feed port of the adsorption unit 8, and the discharge port of the adsorption unit 8 is connected to the nitrate solution collection tank 4. The adsorption unit 8 is an adsorption tower or a stirred tank and a solid-liquid separator connected in series. The first liquid phase separated by the first solid-liquid separator 3 enters the adsorption tower of the adsorption unit 8, and after adsorption and impurity removal, a refined nitrate aqueous solution is obtained. Alternatively, the first liquid phase separated by the first solid-liquid separator 3 enters the stirred tank of the adsorption unit 8, and after adsorption and impurity removal, enters the solid-liquid separator of the adsorption unit 8 to obtain a refined nitrate aqueous solution. The refined nitrate aqueous solution enters the nitrate solution collection tank 4 for temporary storage.

[0062] In this utility model, unless otherwise specified or limited, the communication methods between various units or devices should be understood broadly. For example, communication can be direct pipeline communication, or communication can be through pipelines connected to conventional conveying, metering, control, and temporary storage equipment such as pumping equipment, metering equipment, valves and pipe fittings, intermediate tanks, etc., and communication can be fixed or removable. Those skilled in the art will understand the specific meanings of these terms in this utility model based on specific circumstances.

[0063] In the present invention, various components of the production device, such as the reaction kettle, solid-liquid separator, dissolving kettle, acidifying kettle, stirring kettle, adsorption tower, preheater, separator, rotary drum fluidized bed, tubular reactor, tank reactor, material transfer pump, collection tank, etc. can be purchased from the market, but the entire reaction device cannot be purchased from the market and is not known to those skilled in the art.

[0064] Example 1

[0065] This embodiment provides a comprehensive utilization device containing organic nitric acid, the structural diagram of which is shown in FIG. Figure 1 As shown, it includes an organic nitric acid production unit 1, a neutralization reactor 2, a first solid-liquid separator 3, a nitrate solution collection tank 4, and an organic purification and separation unit 5.

[0066] Among them, the organic nitric acid outlet of the organic nitric acid production unit 1 is connected to the organic nitric acid inlet of the neutralization reactor 2, the neutralization reactor 2 is also provided with an alkaline substance inlet, the outlet of the neutralization reactor 2 is connected to the inlet of the first solid-liquid separator 3, the liquid phase outlet of the first solid-liquid separator 3 is connected to the inlet of the nitrate solution collection tank 4, and the solid phase outlet of the first solid-liquid separator 3 is connected to the inlet of the organic matter purification and separation unit 5.

[0067] The organic nitric acid from the organic nitric acid production unit 1 enters the neutralization reactor 2, undergoes a neutralization reaction with the alkaline substance added to the neutralization reactor 2 to obtain a neutralized liquid. The neutralized liquid enters the first solid-liquid separator 3 for solid-liquid separation to obtain a first solid-phase organic matter and a first liquid-phase nitrate aqueous solution. The first solid-phase organic matter separated by the first solid-liquid separator 3 enters the organic purification and separation unit 5 for further separation and removal of impurities doped in the organic matter, and high-quality organic mononitrated substituted benzoic acid is recovered. The first liquid-phase nitrate aqueous solution separated by the first solid-liquid separator 3 enters the nitrate solution collection tank 4 for storage.

[0068] Example 2

[0069] This embodiment provides a comprehensive utilization device containing organic nitric acid, the structural diagram of which is shown in FIG. Figure 2 As shown, the difference from Example 1 is that the organic matter purification and separation unit 5 of this embodiment is provided with an alkali adjustment kettle 5-1, a second solid-liquid separator 5-2, and an acidification separation unit 6, wherein the acidification separation unit 6 is composed of a first acidification kettle 6-1 and a first acidification liquid-solid-liquid separator 6-2 connected in sequence.

[0070] Among them, the solid phase outlet of the first solid-liquid separator 3 is connected to the inlet of the alkali adjustment kettle 5-1, the alkali adjustment kettle 5-1 is also provided with an alkali liquid inlet, the outlet of the alkali adjustment kettle 5-1 is connected to the inlet of the second solid-liquid separator 5-2, the liquid phase outlet of the second solid-liquid separator 5-2 is connected to the inlet of the first acidifying kettle 6-1, the first acidifying kettle 6-1 is also provided with an acid liquid inlet, and the outlet of the first acidifying kettle 6-1 is connected to the inlet of the first acidifying liquid-solid-liquid separator 6-2.

[0071] On the basis of Example 1, the first solid phase organic matter separated from the first solid-liquid separator 3 enters the alkali adjustment kettle 5-1, and is mixed and reacted with the alkali solution added to the alkali adjustment kettle 5-1. As the reaction proceeds, the mononitrated substituted benzoic acid is converted into a mononitrated substituted benzoate and dissolved in the aqueous solution. The generated reaction liquid flows out of the outlet of the alkali adjustment kettle 5-1 and enters the second solid-liquid separator 5-2 for solid-liquid separation. The solid phase impurities introduced by the alkaline substance are removed to obtain a second liquid phase. The second liquid phase enters the first acidification kettle 6-1 for acid adjustment. During the acid adjustment process, the mononitrated substituted benzoate is converted into mononitrated substituted benzoic acid and precipitated in the form of a solid. The second liquid phase after acid adjustment enters the first acidification liquid-solid-liquid separator 6-2 for solid-liquid separation to obtain the purified organic mononitrated substituted benzoic acid.

[0072] Example 3

[0073] This embodiment provides a comprehensive utilization device containing organic nitric acid, the structural diagram of which is shown in FIG. Figure 3As shown, the difference from Example 2 is that the organic nitric acid production unit 1 in this embodiment consists of a nitration reaction unit 1-1 and a third solid-liquid separator 1-2, and the acidification separation unit 6 consists of a first acidification kettle 6-1, a first acidification liquid-solid-liquid separator 6-2, a second acidification kettle 6-3, a second acidification liquid-solid-liquid separator 6-4, a third acidification kettle 6-5, and a third acidification liquid-solid-liquid separator 6-6, which are connected in sequence. The neutralization reactor 2 is provided with a water inlet, and the nitration reaction unit 1-1 consists of a two-stage kettle reactor.

[0074] The outlet of the nitration reaction unit 1-1 is connected to the inlet of the third solid-liquid separator 1-2, and the liquid phase outlet of the third solid-liquid separator 1-2 is connected to the organic nitric acid inlet of the neutralization reactor 2. The neutralization reactor 2 is also provided with a water inlet. The liquid phase outlet of the second solid-liquid separator 5-2 is connected to the inlet of the first acidification reactor 6-1, which is also provided with an acid liquid inlet. The outlet of the first acidification reactor 6-1 is connected to the inlet of the first acidification liquid-solid-liquid separator 6-2, the liquid phase outlet of the first acidification liquid-solid-liquid separator 6-2 is connected to the inlet of the second acidification reactor 6-3, the outlet of the second acidification reactor 6-3 is connected to the inlet of the second acidification liquid-solid-liquid separator 6-4, the liquid phase outlet of the second acidification liquid-solid-liquid separator 6-4 is connected to the inlet of the third acidification reactor 6-5, and the outlet of the third acidification reactor 6-5 is connected to the inlet of the third acidification liquid-solid-liquid separator 6-6.

[0075] On the basis of Example 2, substituted benzoic acid and excess nitric acid enter the nitration reaction unit 1-1 composed of a two-stage kettle reactor to undergo nitration reaction to obtain a nitration reaction liquid containing mononitrated substituted benzoic acid and nitric acid. The nitration reaction liquid enters the third solid-liquid separator 1-2 to separate the third solid phase mononitrated substituted benzoic acid and the third liquid phase containing organic nitric acid. The organic nitric acid enters the neutralization reactor 2 to undergo a neutralization reaction with an alkaline substance in the presence of additional water to obtain a neutralized liquid. The neutralized liquid enters the first solid-liquid separator 3 for solid-liquid separation to obtain a first solid phase organic matter and a first liquid phase nitrate aqueous solution. After separation in the first solid-liquid separator 3, the organic matter is separated into a first solid phase organic matter and a first liquid phase nitrate aqueous solution. The first liquid phase nitrate aqueous solution separated from the nitrate solution enters the nitrate solution collecting tank 4 for storage, the first solid phase organic matter separated by the first solid-liquid separator 3 enters the alkali adjustment kettle 5-1 of the organic matter purification and separation unit 5, and is mixed with the alkali solution added to the alkali adjustment kettle 5-1 for reaction, and the generated reaction liquid flows out from the outlet of the alkali adjustment kettle 5-1 and enters the second solid-liquid separator 5-2 for solid-liquid separation, and the solid phase impurities are removed to obtain the second liquid phase, and the second liquid phase enters the third-stage acidification and separation unit 6 composed of an acidification kettle and a solid-liquid separator connected in series for three acid adjustment and separation, and is separated by the third acidification liquid-solid-liquid separator 6-6 to obtain the purified organic mononitrated substituted benzoic acid.

[0076] Example 4

[0077] This embodiment provides a comprehensive utilization device containing organic nitric acid, the structural diagram of which is shown in FIG. Figure 4 As shown, the difference from Example 2 is that the organic nitric acid production unit 1 in this embodiment is composed of a nitration reaction unit 1-1, a third solid-liquid separator 1-2, a dilution unit 1-3, and a fourth solid-liquid separator 1-4, and the nitration reaction unit 1-1 is composed of a tubular reactor and a kettle reactor connected in series.

[0078] Among them, the outlet of the nitration reaction unit 1-1 is connected to the inlet of the third solid-liquid separator 1-2, the liquid phase outlet of the third solid-liquid separator 1-2 is connected to the inlet of the dilution unit 1-3, the outlet of the dilution unit 1-3 is connected to the inlet of the fourth solid-liquid separator 1-4, the liquid phase outlet of the fourth solid-liquid separator 1-4 is connected to the organic nitric acid inlet of the neutralization reactor 2, and the neutralization reactor 2 is provided with a water inlet.

[0079] The substituted benzoic acid and excess nitric acid enter the nitration reaction unit 1-1 composed of a tubular reactor and a kettle reactor connected in series to undergo a nitration reaction, thereby obtaining a nitration reaction liquid containing mononitrated substituted benzoic acid and nitric acid. The nitration reaction liquid enters the third solid-liquid separator 1-2 to separate the third solid phase of mononitrated substituted benzoic acid from the third liquid phase. The third liquid phase enters the dilution kettle of the dilution unit 1-3 and is diluted with water. Part of the mononitrated substituted benzoic acid precipitates. The diluted liquid enters the fourth solid-liquid separator 1-4 to separate the fourth solid phase of mononitrated substituted benzoic acid from the fourth liquid phase containing organic nitric acid. The organic nitric acid enters the neutralization reactor 2 and undergoes a neutralization reaction with an alkaline substance in the presence of additional water to obtain a neutralized liquid. Based on Example 2, a nitrate aqueous solution and purified organic mononitrated substituted benzoic acid are obtained.

[0080] Example 5

[0081] This embodiment provides a comprehensive utilization device containing organic nitric acid, the structural diagram of which is shown in FIG. Figure 5 As shown, the difference from Example 4 is that this embodiment is further provided with a nitrate separation unit 7 and an adsorption unit 8. The structural diagram of the nitrate separation unit 7 is shown in FIG. Figure 6 As shown, the nitrate separation unit 7 is composed of a concentration unit 7-1, a transfer pump 7-2, and a granulation unit 7-3. The concentration unit 7-1 is composed of a preheater 7-1-1 and a three-effect separator 7-1-2. The three-effect separator 7-1-2 is composed of a first heater a, a first separation chamber b, a second heater c, a second separation chamber d, a third heater e, and a third separation chamber f. The granulation unit 7-3 uses a rotary drum fluidized bed. The adsorption unit 8 is composed of a stirred tank and a solid-liquid separator connected in series. The nitration reaction unit 1-1 is composed of a two-stage tubular reactor.

[0082] Among them, the outlet of the nitrate solution collecting tank 4 is connected with the inlet of the preheater 7-1-1 in the concentration unit 7-1, the outlet of the preheater 7-1-1 is connected with the inlet of the first heater a, the outlet of the first heater a is connected with the inlet of the first separation chamber b, the concentrated liquid outlet of the first separation chamber b is respectively connected with the inlet of the first heater a and the inlet of the second heater c, the outlet of the second heater c is connected with the inlet of the second separation chamber d, the concentrated liquid outlet of the second separation chamber d is respectively connected with the inlet of the second heater c and the inlet of the third heater e, the outlet of the third heater e is connected with the inlet of the third separation chamber f, and the concentrated liquid outlet of the third separation chamber f is respectively connected with the inlet of the third heater e and the inlet of the granulation unit 7-3 via the transfer pump 7-2.

[0083] On the basis of Example 4, the first liquid phase separated by the first solid-liquid separator 3 enters the stirred tank of the adsorption unit 8, and after adsorption and impurity removal, enters the solid-liquid separator of the adsorption unit 8 to obtain a refined nitrate aqueous solution. The refined nitrate aqueous solution enters the nitrate solution collection tank 4 for temporary storage. The nitrate solution collected in the nitrate solution collection tank 4 is preheated by the preheater 7-1-1 and then enters the triple-effect separator 7-1-2 for concentration. In the triple-effect separator 7-1-2, the preheated nitrate solution is first heated in the first heater a and then enters the first separation chamber b to separate the gas phase to obtain a first concentrated liquid. Part of the first concentrated liquid returns to the first heater a Forced circulation, part of the first concentrated liquid enters the second heater c for heating and then enters the second separation chamber d to separate the gas phase to obtain the second concentrated liquid, part of the second concentrated liquid returns to the second heater c for forced circulation, part of the second concentrated liquid enters the third heater e for heating and then enters the third separation chamber f to separate the gas phase to obtain the third concentrated liquid, part of the third concentrated liquid returns to the third heater e for forced circulation, part of the third concentrated liquid is transported to the drum fluidized bed granulation unit 7-3 through the transfer pump 7-2 for granulation, the granulated solid is screened, the qualified nitrate is collected and packaged, and the unqualified nitrate is cooled and returned to the drum fluidized bed granulation unit 7-3 to continue granulation.

Claims

1. A comprehensive utilization device containing organic nitric acid, characterized in that: It comprises an organic nitric acid generating unit (1), a neutralization reactor (2), a first solid-liquid separator (3) and an organic purification and separation unit (5); The organic nitric acid outlet of the organic nitric acid generating unit (1) is connected to the organic nitric acid inlet of the neutralization reactor (2), the outlet of the neutralization reactor (2) is connected to the inlet of the first solid-liquid separator (3), the liquid phase outlet of the first solid-liquid separator (3) is connected to the inlet of the nitrate solution collecting tank (4); the solid phase outlet of the first solid-liquid separator (3) is connected to the inlet of the organic matter purification and separation unit (5); The neutralization reactor (2) is also provided with an alkaline substance inlet.

2. The comprehensive utilization device containing organic nitric acid according to claim 1, characterized in that: The organic matter purification and separation unit (5) comprises an alkali adjustment kettle (5-1), a second solid-liquid separator (5-2) and an acidification separation unit (6) which are connected in sequence; The acidification separation unit (6) comprises at least one primary acidification separation subunit; the acidification separation subunit comprises an acidification kettle and an acidification liquid-solid-liquid separator connected in sequence; The outlet of the alkali adjustment kettle (5-1) is connected to the acidification kettle, and the alkali adjustment kettle (5-1) is also provided with an alkali solution inlet; The acidification kettle is also provided with an acid liquid inlet.

3. The comprehensive utilization device containing organic nitric acid according to claim 1, characterized in that: The neutralization reactor (2) is also provided with a water inlet.

4. The comprehensive utilization device containing organic nitric acid according to claim 1, characterized in that: The organic nitric acid production unit (1) comprises a nitration reaction unit (1-1) and a third solid-liquid separator (1-2) connected in sequence; The liquid phase outlet of the third solid-liquid separator (1-2) is connected to the organic nitric acid inlet of the neutralization reactor (2).

5. The comprehensive utilization device containing organic nitric acid according to claim 4, characterized in that: The organic nitric acid production unit (1) further includes a dilution unit (1-3) and a fourth solid-liquid separator (1-4) connected in sequence; The liquid phase outlet of the third solid-liquid separator (1-2) is connected to the inlet of the dilution unit (1-3), the outlet of the dilution unit (1-3) is connected to the inlet of the fourth solid-liquid separator (1-4), and the liquid phase outlet of the fourth solid-liquid separator (1-4) is connected to the organic nitric acid inlet of the neutralization reactor (2).

6. The comprehensive utilization device containing organic nitric acid according to claim 4 or 5, characterized in that: The nitration reaction unit (1-1) includes at least one primary reactor, and the reactor includes a tubular reactor, a tank reactor, or a tubular reactor and a tank reactor connected in series.

7. The comprehensive utilization device containing organic nitric acid according to claim 1, characterized in that: The comprehensive utilization device further includes a nitrate separation unit (7); The inlet of the nitrate separation unit (7) is connected to the outlet of the nitrate solution collection tank (4).

8. The comprehensive utilization device containing organic nitric acid according to claim 7, characterized in that: The nitrate separation unit (7) comprises a concentration unit (7-1), a material transfer pump (7-2) and a granulation unit (7-3) which are connected in sequence; The inlet of the concentration unit (7-1) is connected to the outlet of the nitrate solution collection tank (4).

9. The comprehensive utilization device containing organic nitric acid according to claim 8, characterized in that: The concentration unit (7-1) comprises a preheater (7-1-1) and a separation device connected in series, wherein the separation device is at least a single-effect separator; and the separator comprises a heater and a separation chamber connected in series.

10. The comprehensive utilization device containing organic nitric acid according to claim 1, characterized in that: The comprehensive utilization device further includes an adsorption unit (8); The liquid phase outlet of the first solid-liquid separator (3) is connected to the feed port of the adsorption unit (8), and the discharge port of the adsorption unit (8) is connected to the inlet of the nitrate solution collection tank (4).

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