CN111268843A - Process for recovering nitric acid from nitrified wastewater - Google Patents
Process for recovering nitric acid from nitrified wastewater Download PDFInfo
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- CN111268843A CN111268843A CN202010128560.0A CN202010128560A CN111268843A CN 111268843 A CN111268843 A CN 111268843A CN 202010128560 A CN202010128560 A CN 202010128560A CN 111268843 A CN111268843 A CN 111268843A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/38—Nitric acid
- C01B21/46—Purification; Separation ; Stabilisation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
- C02F1/06—Flash evaporation
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
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- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F2001/007—Processes including a sedimentation step
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
Abstract
The invention relates to the technical field of nitric acid recovery, in particular to a process for recovering nitric acid from nitrified wastewater, which can conveniently recycle the residual nitric acid in the nitrified wastewater, degrade economic loss and reduce corrosion to equipment; the method comprises the following steps: s1, standing and layering; s2, filtering; s3, performing primary cyclic adsorption; s4, reduced pressure distillation: sealing the treatment equipment, reducing the pressure in the treatment equipment to 1.33-2.60 kPa, controlling the heating temperature of the treatment equipment to be 30-40 ℃, and carrying out reduced pressure distillation on the wastewater in the treatment equipment until the distilled part is not increased any more; s5, secondary cycle adsorption: after the reduced pressure distillation is finished, continuously performing in vivo circulation on the residual waste liquid in the treatment equipment, and performing secondary adsorption circulation treatment for 15-25 min by using adsorption resin; s6, boosting: controlling the interior of the processing equipment to carry out boosting treatment, and keeping the temperature in the processing equipment stable in the boosting process; and S7, recovering the feed liquid.
Description
Technical Field
The invention relates to the technical field of nitric acid recovery, in particular to a process for recovering nitric acid from nitrified wastewater.
Background
It is well known that nitration is towards organic moleculesThe reaction process of introducing the nitro group is characterized in that an oxidation-bond breaking side reaction is generated during the nitration of the aliphatic compound, the nitro group is a univalent group formed by the loss of one hydroxyl group of the nitric acid, and the reaction mechanism of the nitration of the aromatic compound is as follows: the-OH group of nitric acid is protonated, followed by dehydration of one molecule of water by a dehydrating agent to form a nitroxyl positive ion (NO)2) The intermediate and the benzene ring carry out electrophilic aromatic substitution reaction finally, and remove one molecule of hydrogen ions, the nitration reaction is one of the important unit reactions in the organic chemical industry, the nitration product has very wide application, not only plays an important role in civil industries such as dye, pharmacy and the like, but also plays an important role in the national defense industry, therefore, the nitration reaction is a common reaction in the pharmaceutical process, after the nitration reaction is completed, the organic phase is separated, the excessive nitric acid remains in the sulfuric acid, namely the nitration waste acid is formed, in order to facilitate the subsequent use of the residual nitric acid and the sulfuric acid, impurities, moisture and the like in the residual nitric acid and the sulfuric acid are usually required to be removed, the existing common removal mode is evaporation concentration under the negative pressure state to remove the moisture, and simultaneously, the nitric acid in the nitration waste water is removed through hot air bubbling, but nitrogen oxides and water are introduced in the removal process, the method is easy to corrode equipment, most of nitric acid in the equipment is wasted and cannot be recycled, and therefore certain economic loss can be caused in the process of treating the nitrified wastewater.
Disclosure of Invention
In order to solve the technical problems, the invention provides the nitric acid recovery process in the nitrifying wastewater, which can conveniently recycle the residual nitric acid in the nitrifying wastewater, degrade the economic loss and reduce the corrosion to equipment.
The invention relates to a process for recovering nitric acid from nitrifying wastewater, which comprises the following steps:
s1, standing and layering: introducing the wastewater generated by the nitration reaction into temporary storage equipment for standing, keeping the temperature of the wastewater between 30 and 40 ℃, and standing for 50 to 70min to perform solid-liquid separation on the wastewater;
s2, filtering: pumping out the supernatant of the layered nitrifying wastewater, and filtering by using a filtering device until the supernatant is completely pumped out;
s3, primary cycle adsorption: introducing the filtered supernatant into treatment equipment, adsorbing the filtered supernatant by using adsorption resin, and controlling the treatment equipment to perform internal circulation so that the filtered supernatant is repeatedly subjected to primary adsorption circulation treatment for 15-25 min by using the adsorption resin;
s4, reduced pressure distillation: sealing the treatment equipment, carrying out reduced pressure treatment on the treatment equipment, reducing the pressure in the treatment equipment to 1.33-2.60 kPa, controlling the heating temperature of the treatment equipment to be 30-40 ℃, and carrying out reduced pressure distillation on the wastewater in the treatment equipment until the distilled part is not increased any more;
s5, secondary cycle adsorption: after the reduced pressure distillation is finished, continuously performing in vivo circulation on the residual waste liquid in the treatment equipment, and performing secondary adsorption circulation treatment for 15-25 min by using adsorption resin;
s6, boosting: controlling the interior of the processing equipment to carry out boosting treatment, so that the interior of the processing equipment is recovered to a normal pressure state, and in the boosting process, keeping the temperature inside the processing equipment stable, and reducing temperature change;
s7, feed liquid recovery: and finally, residual liquid in the treatment equipment is discharged and recycled, so that the treatment equipment is convenient to recycle.
Further, the filtering medium in the filtering device used in the step S2 is a molecular sieve, and the filling thickness of the molecular sieve is 15-25 cm.
Further, the adsorption resin is macroporous adsorption resin, and the basic raw materials of the adsorption resin are styrene and propionate.
Further, the adsorption resin is prepared from the following raw materials in percentage by mass:
10-15 parts of styrene;
12-16 parts of propionate;
1-3 parts of styrene;
0.5-0.9 part of toluene;
0.3-0.8 part of dimethylbenzene.
Further, the preparation process of the adsorption resin comprises the following steps: styrene and acrylic acid were added to a 0.5% gelatin solution, and styrene was added thereto, and toluene and xylene were added thereto to form a pore skeleton structure by mutual crosslinking.
Further, the process for recovering nitric acid from nitrified wastewater is based on a recovery device, and comprises a recovery box, two sets of partition nets, adsorption resin, a communicating pipe, a circulating pump, a separation barrel, a first transmission pipe, a U-shaped filter barrel, a second transmission pipe, a liquid pump, a sealing cover, a plurality of sets of supporting legs and a liquid discharge pipe, wherein a recovery cavity is arranged in the recovery box, a cleaning port is communicated with the top of the recovery box and communicated with the recovery cavity, the sealing cover is arranged at the top of the recovery box and provided with two sets of fixing holes and air exchange holes, the inner walls of the two sets of fixing holes are respectively provided with a vacuum pipe and a discharge pipe, switch valves are respectively arranged on the vacuum pipe and the discharge pipe, the two sets of partition nets are transversely arranged in the recovery box, the adsorption resin is positioned between the two sets of partition nets, and two ends of the vacuum pipe are respectively communicated with the upper half area and the lower half area, the circulating pump is installed on the communicating pipe, a separation cavity is arranged in the separation barrel, a liquid filling opening is arranged at the top of the separation barrel in a communicated mode, the input end of the first transmission pipe penetrates through the side wall of the separation barrel and extends into the separation barrel, the liquid suction pump is installed on the first transmission pipe, a filter cavity is arranged in the U-shaped filter barrel, the output end of the first transmission pipe is communicated with the U-shaped filter barrel, two ends of the second transmission pipe are respectively communicated with the U-shaped filter barrel and the recovery box, a control valve is arranged on the second transmission pipe, the U-shaped filter barrel is filled with the molecular sieve, the multiple groups of supporting legs are all installed at the bottom of the recovery box, the liquid discharge pipe is communicated with the bottom of the recovery box, a discharge valve is arranged on the liquid discharge pipe, and.
Furthermore, recovery plant still includes multiunit bracing piece and multiunit supporting shoe, multiunit bracing piece both ends are connected with multiunit supporting shoe and the bottom in the collection box respectively, multiunit supporting shoe all with be located the downside separate the net bottom contact.
Furthermore, the outer wall of the recovery device is wrapped with a temperature control layer.
Compared with the prior art, the invention has the beneficial effects that: when the process is used for treating the nitrified wastewater, firstly, impurities in the nitrified wastewater are settled through standing separation, the nitrified wastewater is filtered through a molecular sieve, the wastewater is subjected to physical adsorption treatment by adopting the huge specific surface area of the adsorption resin, so that residual organic matters and the like in the nitrified wastewater can be adsorbed and separated, and finally, the nitrified wastewater is recovered through a reduced pressure distillation mode, so that the residual nitric acid in the nitrified wastewater can be conveniently recycled, the economic loss is reduced, the corrosion to equipment can be reduced, the obtained recovered liquid has no nitric acid and byproducts thereof evaporated, and nitrogen oxide and water are not introduced, and the recovery rate of the nitric acid reaches over 95 percent.
Drawings
FIG. 1 is a flow diagram of the recovery process of the present invention;
FIG. 2 is a schematic view of a part of the recycling apparatus used in the recycling process of the present invention;
in the drawings, the reference numbers: 1. a recycling bin; 2. separating the net; 3. an adsorbent resin; 4. a communicating pipe; 5. a circulation pump; 6. a separation barrel; 7. a first transfer tube; 8. a U-shaped filter barrel; 9. a second transfer pipe; 10. a liquid pump; 11. a sealing cover; 12. a support leg; 13. a liquid discharge pipe; 14. vacuumizing a tube; 15. a discharge pipe; 16. an on-off valve; 17. a control valve; 18. a molecular sieve; 19. a discharge valve; 20. a scavenging valve; 21. a support bar; 22. a support block; 23. a temperature control layer.
Detailed Description
The following detailed description of the embodiments of the present invention is provided in connection with the accompanying drawings and examples. The following examples are intended to illustrate the invention but are not intended to limit the scope of the invention.
Example 1
Preparing an adsorbent resin: 10 parts of styrene and 12 parts of acrylic acid were added to a 0.5% gelatin solution, and 1 part of styrene was added thereto, followed by addition of 0.5 part of toluene and 0.3 part of xylene, to crosslink with each other to form a pore skeleton structure.
A process for recovering nitric acid from nitrified wastewater comprises the following steps:
s1, standing and layering: introducing the wastewater generated by the nitration reaction into a temporary storage device for standing, keeping the temperature at about 32 ℃, and standing for 55min to perform solid-liquid separation on the wastewater;
s2, filtering: pumping the supernatant of the layered nitrifying wastewater, and filtering by using a filtering device until the supernatant is completely pumped out, wherein a filtering medium in the filtering device is a molecular sieve, and the filling thickness of the molecular sieve is 15 cm;
s3, primary cycle adsorption: introducing the filtered supernatant into a treatment device, allowing the supernatant to pass through an adsorption resin for adsorption, and controlling the supernatant to perform internal circulation of the device, so that the supernatant repeatedly passes through the adsorption resin for primary adsorption circulation treatment for 15 min;
s4, reduced pressure distillation: sealing the treatment equipment, carrying out reduced pressure treatment on the treatment equipment, reducing the pressure in the treatment equipment to 1.33kPa, controlling the heating temperature of the treatment equipment to be 40 ℃, and carrying out reduced pressure distillation on the wastewater in the treatment equipment until the distilled part is not increased any more;
s5, secondary cycle adsorption: after the reduced pressure distillation is finished, the residual waste liquid in the treatment equipment is continuously subjected to in vivo circulation, and the secondary adsorption circulation treatment is carried out for 15min by using adsorption resin;
s6, boosting: controlling the interior of the processing equipment to carry out boosting treatment, so that the interior of the processing equipment is recovered to a normal pressure state, and in the boosting process, keeping the temperature inside the processing equipment stable, and reducing temperature change;
s7, feed liquid recovery: and finally, residual liquid in the treatment equipment is discharged and recycled, so that the treatment equipment is convenient to recycle.
The nitric acid recovery process in the nitrified wastewater is based on a recovery device, the device comprises a recovery box 1, two groups of partition nets 2, adsorption resin 3, a communicating pipe 4, a circulating pump 5, a separation barrel 6, a first transmission pipe 7, a U-shaped filter barrel 8, a second transmission pipe 9, a liquid pump 10, a sealing cover 11, a plurality of groups of supporting legs 12 and a liquid discharge pipe 13, wherein a recovery cavity is arranged in the recovery box 1, a cleaning port is communicated and arranged at the top of the recovery box 1 and communicated with the recovery cavity, the sealing cover 11 is arranged at the top of the recovery box 1 and provided with two groups of fixing holes and ventilating holes, the inner walls of the two groups of fixing holes are respectively provided with a vacuum pumping pipe 14 and a discharge pipe 15, switch valves 16 are respectively arranged on the vacuum pumping pipe 14 and the discharge pipe 15, the two groups of partition nets 2 are transversely arranged in the recovery box 1, the adsorption resin 3 is positioned between the two groups of partition nets 2, the two ends of the communicating pipe 4 are respectively communicated, the circulating pump 5 is arranged on the communicating pipe 4, a separation cavity is arranged in the separation barrel 6, the top of the separation barrel 6 is communicated and provided with a liquid filling port, the input end of the first transmission pipe 7 penetrates through the side wall of the separation barrel 6 and extends into the separation barrel 6, the liquid pump 10 is arranged on the first transmission pipe 7, the U-shaped filter barrel 8 is internally provided with a filter cavity, the output end of the first transmission pipe 7 is communicated with the U-shaped filter barrel 8, the two ends of the second transmission pipe 9 are respectively communicated with the U-shaped filter barrel 8 and the recovery box 1, the second transmission pipe 9 is provided with a control valve 17, the U-shaped filter barrel 8 is filled with a molecular sieve 18, a plurality of groups of support legs 12 are respectively arranged at the bottom of the recovery box 1, the liquid discharge pipe 13 is communicated with the bottom of the recovery box 1, the liquid discharge pipe 13 is provided with a discharge valve 19, the gas exchange valve 20 is arranged at the gas exchange hole, the multi-group support rods 21 and, the multiple groups of supporting blocks 22 are all contacted with the bottom of the separation net 2 positioned on the lower side, and the outer wall of the recovery equipment is wrapped with a temperature control layer 23.
The recovered liquid obtained by the embodiment has no evaporated nitric acid and byproducts thereof, and nitrogen oxide and water are not introduced, the recovery rate of the nitric acid reaches over 95 percent, the residual nitric acid in the nitrification wastewater is convenient to recycle, the economic loss is reduced, and the corrosion to equipment can be reduced.
Example 2
Preparing an adsorbent resin: 12 parts of styrene and 13 parts of acrylic acid were added to a 0.5% gelatin solution, and 1.5 parts of styrene, 0.6 part of toluene and 0.4 part of xylene were added thereto to crosslink with each other to form a pore skeleton structure.
A process for recovering nitric acid from nitrified wastewater comprises the following steps:
s1, standing and layering: introducing the wastewater generated by the nitration reaction into temporary storage equipment for standing, keeping the temperature at about 35 ℃, and standing for 70min to perform solid-liquid separation on the wastewater;
s2, filtering: pumping the supernatant of the layered nitrifying wastewater, and filtering by using a filtering device until the supernatant is completely pumped out, wherein a filtering medium in the filtering device is a molecular sieve, and the filling thickness of the molecular sieve is 19 cm;
s3, primary cycle adsorption: introducing the filtered supernatant into a treatment device, allowing the supernatant to pass through an adsorption resin for adsorption, and controlling the supernatant to perform internal circulation of the device, so that the supernatant repeatedly passes through the adsorption resin for one-time adsorption circulation treatment for 25 min;
s4, reduced pressure distillation: sealing the treatment equipment, carrying out reduced pressure treatment on the treatment equipment, reducing the pressure in the treatment equipment to 2.60kPa, controlling the heating temperature of the treatment equipment to be 30 ℃, and carrying out reduced pressure distillation on the wastewater in the treatment equipment until the distilled part is not increased any more;
s5, secondary cycle adsorption: after the reduced pressure distillation is finished, the residual waste liquid in the treatment equipment is continuously subjected to in vivo circulation, and the secondary adsorption circulation treatment is carried out for 20min by using adsorption resin;
s6, boosting: controlling the interior of the processing equipment to carry out boosting treatment, so that the interior of the processing equipment is recovered to a normal pressure state, and in the boosting process, keeping the temperature inside the processing equipment stable, and reducing temperature change;
s7, feed liquid recovery: and finally, residual liquid in the treatment equipment is discharged and recycled, so that the treatment equipment is convenient to recycle.
The nitric acid recovery process in the nitrified wastewater is based on a recovery device, the device comprises a recovery box 1, two groups of partition nets 2, adsorption resin 3, a communicating pipe 4, a circulating pump 5, a separation barrel 6, a first transmission pipe 7, a U-shaped filter barrel 8, a second transmission pipe 9, a liquid pump 10, a sealing cover 11, a plurality of groups of supporting legs 12 and a liquid discharge pipe 13, wherein a recovery cavity is arranged in the recovery box 1, a cleaning port is communicated and arranged at the top of the recovery box 1 and communicated with the recovery cavity, the sealing cover 11 is arranged at the top of the recovery box 1 and provided with two groups of fixing holes and ventilating holes, the inner walls of the two groups of fixing holes are respectively provided with a vacuum pumping pipe 14 and a discharge pipe 15, switch valves 16 are respectively arranged on the vacuum pumping pipe 14 and the discharge pipe 15, the two groups of partition nets 2 are transversely arranged in the recovery box 1, the adsorption resin 3 is positioned between the two groups of partition nets 2, the two ends of the communicating pipe 4 are respectively communicated, the circulating pump 5 is arranged on the communicating pipe 4, a separation cavity is arranged in the separation barrel 6, the top of the separation barrel 6 is communicated and provided with a liquid filling port, the input end of the first transmission pipe 7 penetrates through the side wall of the separation barrel 6 and extends into the separation barrel 6, the liquid pump 10 is arranged on the first transmission pipe 7, the U-shaped filter barrel 8 is internally provided with a filter cavity, the output end of the first transmission pipe 7 is communicated with the U-shaped filter barrel 8, the two ends of the second transmission pipe 9 are respectively communicated with the U-shaped filter barrel 8 and the recovery box 1, the second transmission pipe 9 is provided with a control valve 17, the U-shaped filter barrel 8 is filled with a molecular sieve 18, a plurality of groups of support legs 12 are respectively arranged at the bottom of the recovery box 1, the liquid discharge pipe 13 is communicated with the bottom of the recovery box 1, the liquid discharge pipe 13 is provided with a discharge valve 19, the gas exchange valve 20 is arranged at the gas exchange hole, the multi-group support rods 21 and, the multiple groups of supporting blocks 22 are all contacted with the bottom of the separation net 2 positioned on the lower side, and the outer wall of the recovery equipment is wrapped with a temperature control layer 23.
The recovered liquid obtained by the embodiment has no evaporated nitric acid and byproducts thereof, and nitrogen oxide and water are not introduced, the recovery rate of the nitric acid reaches over 95 percent, the residual nitric acid in the nitrification wastewater is convenient to recycle, the economic loss is reduced, and the corrosion to equipment can be reduced.
Example 3
Preparing an adsorbent resin: 13 parts of styrene and 14 parts of acrylic acid were added to a 0.5% gelatin solution, and 2 parts of styrene was added thereto, followed by addition of 0.7 part of toluene and 0.6 part of xylene, to crosslink with each other to form a pore skeleton structure.
A process for recovering nitric acid from nitrified wastewater comprises the following steps:
s1, standing and layering: introducing the wastewater generated by the nitration reaction into temporary storage equipment for standing, keeping the temperature at about 38 ℃, and standing for 60min to perform solid-liquid separation on the wastewater;
s2, filtering: pumping the supernatant of the layered nitrifying wastewater, and filtering by using a filtering device until the supernatant is completely pumped out, wherein a filtering medium in the filtering device is a molecular sieve, and the filling thickness of the molecular sieve is 25 cm;
s3, primary cycle adsorption: introducing the filtered supernatant into a treatment device, allowing the supernatant to pass through an adsorption resin for adsorption, and controlling the supernatant to perform internal circulation of the device, so that the supernatant repeatedly passes through the adsorption resin for one-time adsorption circulation treatment for 25 min;
s4, reduced pressure distillation: sealing the treatment equipment, carrying out reduced pressure treatment on the treatment equipment, reducing the pressure in the treatment equipment to 2kPa, controlling the heating temperature of the treatment equipment to be 35 ℃, and carrying out reduced pressure distillation on the wastewater in the treatment equipment until the distilled part is not increased any more;
s5, secondary cycle adsorption: after the reduced pressure distillation is finished, the residual waste liquid in the treatment equipment is continuously subjected to in vivo circulation, and the secondary adsorption circulation treatment is carried out for 20min by using adsorption resin;
s6, boosting: controlling the interior of the processing equipment to carry out boosting treatment, so that the interior of the processing equipment is recovered to a normal pressure state, and in the boosting process, keeping the temperature inside the processing equipment stable, and reducing temperature change;
s7, feed liquid recovery: and finally, residual liquid in the treatment equipment is discharged and recycled, so that the treatment equipment is convenient to recycle.
The nitric acid recovery process in the nitrified wastewater is based on a recovery device, the device comprises a recovery box 1, two groups of partition nets 2, adsorption resin 3, a communicating pipe 4, a circulating pump 5, a separation barrel 6, a first transmission pipe 7, a U-shaped filter barrel 8, a second transmission pipe 9, a liquid pump 10, a sealing cover 11, a plurality of groups of supporting legs 12 and a liquid discharge pipe 13, wherein a recovery cavity is arranged in the recovery box 1, a cleaning port is communicated and arranged at the top of the recovery box 1 and communicated with the recovery cavity, the sealing cover 11 is arranged at the top of the recovery box 1 and provided with two groups of fixing holes and ventilating holes, the inner walls of the two groups of fixing holes are respectively provided with a vacuum pumping pipe 14 and a discharge pipe 15, switch valves 16 are respectively arranged on the vacuum pumping pipe 14 and the discharge pipe 15, the two groups of partition nets 2 are transversely arranged in the recovery box 1, the adsorption resin 3 is positioned between the two groups of partition nets 2, the two ends of the communicating pipe 4 are respectively communicated, the circulating pump 5 is arranged on the communicating pipe 4, a separation cavity is arranged in the separation barrel 6, the top of the separation barrel 6 is communicated and provided with a liquid filling port, the input end of the first transmission pipe 7 penetrates through the side wall of the separation barrel 6 and extends into the separation barrel 6, the liquid pump 10 is arranged on the first transmission pipe 7, the U-shaped filter barrel 8 is internally provided with a filter cavity, the output end of the first transmission pipe 7 is communicated with the U-shaped filter barrel 8, the two ends of the second transmission pipe 9 are respectively communicated with the U-shaped filter barrel 8 and the recovery box 1, the second transmission pipe 9 is provided with a control valve 17, the U-shaped filter barrel 8 is filled with a molecular sieve 18, a plurality of groups of support legs 12 are respectively arranged at the bottom of the recovery box 1, the liquid discharge pipe 13 is communicated with the bottom of the recovery box 1, the liquid discharge pipe 13 is provided with a discharge valve 19, the gas exchange valve 20 is arranged at the gas exchange hole, the multi-group support rods 21 and, the multiple groups of supporting blocks 22 are all contacted with the bottom of the separation net 2 positioned on the lower side, and the outer wall of the recovery equipment is wrapped with a temperature control layer 23.
The recovered liquid obtained by the embodiment has no evaporated nitric acid and byproducts thereof, and nitrogen oxide and water are not introduced, the recovery rate of the nitric acid reaches over 95 percent, the residual nitric acid in the nitrification wastewater is convenient to recycle, the economic loss is reduced, and the corrosion to equipment can be reduced.
Example 4
Preparing an adsorbent resin: 14 parts of styrene and 15 parts of acrylic acid were added to a 0.5% gelatin solution, and 2.5 parts of styrene, 0.8 part of toluene and 0.7 part of xylene were added thereto to crosslink with each other to form a pore skeleton structure.
A process for recovering nitric acid from nitrified wastewater comprises the following steps:
s1, standing and layering: introducing the wastewater generated by the nitration reaction into a temporary storage device for standing, keeping the temperature of the wastewater at 30 ℃, and standing for 65min to perform solid-liquid separation on the wastewater;
s2, filtering: pumping the supernatant of the layered nitrifying wastewater, and filtering by using a filtering device until the supernatant is completely pumped out, wherein a filtering medium in the filtering device is a molecular sieve, and the filling thickness of the molecular sieve is 22 cm;
s3, primary cycle adsorption: introducing the filtered supernatant into a treatment device, allowing the supernatant to pass through an adsorption resin for adsorption, and controlling the supernatant to perform internal circulation of the device, so that the supernatant repeatedly passes through the adsorption resin for primary adsorption circulation treatment for 22 min;
s4, reduced pressure distillation: sealing the treatment equipment, carrying out reduced pressure treatment on the treatment equipment, reducing the pressure in the treatment equipment to 1.80kPa, controlling the heating temperature of the treatment equipment to be 38 ℃, and carrying out reduced pressure distillation on the wastewater in the treatment equipment until the distilled part is not increased any more;
s5, secondary cycle adsorption: after the reduced pressure distillation is finished, the residual waste liquid in the treatment equipment is continuously subjected to in vivo circulation, and the secondary adsorption circulation treatment is carried out for 18min by using adsorption resin;
s6, boosting: controlling the interior of the processing equipment to carry out boosting treatment, so that the interior of the processing equipment is recovered to a normal pressure state, and in the boosting process, keeping the temperature inside the processing equipment stable, and reducing temperature change;
s7, feed liquid recovery: and finally, residual liquid in the treatment equipment is discharged and recycled, so that the treatment equipment is convenient to recycle.
The nitric acid recovery process in the nitrified wastewater is based on a recovery device, the device comprises a recovery box 1, two groups of partition nets 2, adsorption resin 3, a communicating pipe 4, a circulating pump 5, a separation barrel 6, a first transmission pipe 7, a U-shaped filter barrel 8, a second transmission pipe 9, a liquid pump 10, a sealing cover 11, a plurality of groups of supporting legs 12 and a liquid discharge pipe 13, wherein a recovery cavity is arranged in the recovery box 1, a cleaning port is communicated and arranged at the top of the recovery box 1 and communicated with the recovery cavity, the sealing cover 11 is arranged at the top of the recovery box 1 and provided with two groups of fixing holes and ventilating holes, the inner walls of the two groups of fixing holes are respectively provided with a vacuum pumping pipe 14 and a discharge pipe 15, switch valves 16 are respectively arranged on the vacuum pumping pipe 14 and the discharge pipe 15, the two groups of partition nets 2 are transversely arranged in the recovery box 1, the adsorption resin 3 is positioned between the two groups of partition nets 2, the two ends of the communicating pipe 4 are respectively communicated, the circulating pump 5 is arranged on the communicating pipe 4, a separation cavity is arranged in the separation barrel 6, the top of the separation barrel 6 is communicated and provided with a liquid filling port, the input end of the first transmission pipe 7 penetrates through the side wall of the separation barrel 6 and extends into the separation barrel 6, the liquid pump 10 is arranged on the first transmission pipe 7, the U-shaped filter barrel 8 is internally provided with a filter cavity, the output end of the first transmission pipe 7 is communicated with the U-shaped filter barrel 8, the two ends of the second transmission pipe 9 are respectively communicated with the U-shaped filter barrel 8 and the recovery box 1, the second transmission pipe 9 is provided with a control valve 17, the U-shaped filter barrel 8 is filled with a molecular sieve 18, a plurality of groups of support legs 12 are respectively arranged at the bottom of the recovery box 1, the liquid discharge pipe 13 is communicated with the bottom of the recovery box 1, the liquid discharge pipe 13 is provided with a discharge valve 19, the gas exchange valve 20 is arranged at the gas exchange hole, the multi-group support rods 21 and, the multiple groups of supporting blocks 22 are all contacted with the bottom of the separation net 2 positioned on the lower side, and the outer wall of the recovery equipment is wrapped with a temperature control layer 23.
The recovered liquid obtained by the embodiment has no evaporated nitric acid and byproducts thereof, and nitrogen oxide and water are not introduced, the recovery rate of the nitric acid reaches over 95 percent, the residual nitric acid in the nitrification wastewater is convenient to recycle, the economic loss is reduced, and the corrosion to equipment can be reduced.
Example 5
Preparing an adsorbent resin: 15 parts of styrene and 16 parts of acrylic acid were added to a 0.5% gelatin solution, and 3 parts of styrene, 0.9 part of toluene and 0.8 part of xylene were added thereto to crosslink with each other to form a pore skeleton structure.
A process for recovering nitric acid from nitrified wastewater comprises the following steps:
s1, standing and layering: introducing the wastewater generated by the nitration reaction into temporary storage equipment for standing, keeping the temperature at 30 ℃, and standing for 70min to perform solid-liquid separation on the wastewater;
s2, filtering: pumping the supernatant of the layered nitrifying wastewater, and filtering by using a filtering device until the supernatant is completely pumped out, wherein a filtering medium in the filtering device is a molecular sieve, and the filling thickness of the molecular sieve is 18 cm;
s3, primary cycle adsorption: introducing the filtered supernatant into a treatment device, allowing the supernatant to pass through an adsorption resin for adsorption, and controlling the supernatant to perform internal circulation of the device, so that the supernatant repeatedly passes through the adsorption resin for one-time adsorption circulation treatment for 18 min;
s4, reduced pressure distillation: sealing the treatment equipment, carrying out reduced pressure treatment on the treatment equipment, reducing the pressure in the treatment equipment to 2.35kPa, controlling the heating temperature of the treatment equipment to be 32 ℃, and carrying out reduced pressure distillation on the wastewater in the treatment equipment until the distilled part is not increased any more;
s5, secondary cycle adsorption: after the reduced pressure distillation is finished, the residual waste liquid in the treatment equipment is continuously subjected to in vivo circulation, and the secondary adsorption circulation treatment is carried out for 22min by using adsorption resin;
s6, boosting: controlling the interior of the processing equipment to carry out boosting treatment, so that the interior of the processing equipment is recovered to a normal pressure state, and in the boosting process, keeping the temperature inside the processing equipment stable, and reducing temperature change;
s7, feed liquid recovery: and finally, residual liquid in the treatment equipment is discharged and recycled, so that the treatment equipment is convenient to recycle.
The nitric acid recovery process in the nitrified wastewater is based on a recovery device, the device comprises a recovery box 1, two groups of partition nets 2, adsorption resin 3, a communicating pipe 4, a circulating pump 5, a separation barrel 6, a first transmission pipe 7, a U-shaped filter barrel 8, a second transmission pipe 9, a liquid pump 10, a sealing cover 11, a plurality of groups of supporting legs 12 and a liquid discharge pipe 13, wherein a recovery cavity is arranged in the recovery box 1, a cleaning port is communicated and arranged at the top of the recovery box 1 and communicated with the recovery cavity, the sealing cover 11 is arranged at the top of the recovery box 1 and provided with two groups of fixing holes and ventilating holes, the inner walls of the two groups of fixing holes are respectively provided with a vacuum pumping pipe 14 and a discharge pipe 15, switch valves 16 are respectively arranged on the vacuum pumping pipe 14 and the discharge pipe 15, the two groups of partition nets 2 are transversely arranged in the recovery box 1, the adsorption resin 3 is positioned between the two groups of partition nets 2, the two ends of the communicating pipe 4 are respectively communicated, the circulating pump 5 is arranged on the communicating pipe 4, a separation cavity is arranged in the separation barrel 6, the top of the separation barrel 6 is communicated and provided with a liquid filling port, the input end of the first transmission pipe 7 penetrates through the side wall of the separation barrel 6 and extends into the separation barrel 6, the liquid pump 10 is arranged on the first transmission pipe 7, the U-shaped filter barrel 8 is internally provided with a filter cavity, the output end of the first transmission pipe 7 is communicated with the U-shaped filter barrel 8, the two ends of the second transmission pipe 9 are respectively communicated with the U-shaped filter barrel 8 and the recovery box 1, the second transmission pipe 9 is provided with a control valve 17, the U-shaped filter barrel 8 is filled with a molecular sieve 18, a plurality of groups of support legs 12 are respectively arranged at the bottom of the recovery box 1, the liquid discharge pipe 13 is communicated with the bottom of the recovery box 1, the liquid discharge pipe 13 is provided with a discharge valve 19, the gas exchange valve 20 is arranged at the gas exchange hole, the multi-group support rods 21 and, the multiple groups of supporting blocks 22 are all contacted with the bottom of the separation net 2 positioned on the lower side, and the outer wall of the recovery equipment is wrapped with a temperature control layer 23.
The recovered liquid obtained by the embodiment has no evaporated nitric acid and byproducts thereof, and nitrogen oxide and water are not introduced, the recovery rate of the nitric acid reaches over 95 percent, the residual nitric acid in the nitrification wastewater is convenient to recycle, the economic loss is reduced, and the corrosion to equipment can be reduced.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and variations can be made without departing from the technical principle of the present invention, and these modifications and variations should also be regarded as the protection scope of the present invention.
Claims (8)
1. A process for recovering nitric acid from nitrified wastewater is characterized by comprising the following steps:
s1, standing and layering: introducing the wastewater generated by the nitration reaction into temporary storage equipment for standing, keeping the temperature of the wastewater between 30 and 40 ℃, and standing for 50 to 70min to perform solid-liquid separation on the wastewater;
s2, filtering: pumping out the supernatant of the layered nitrifying wastewater, and filtering by using a filtering device until the supernatant is completely pumped out;
s3, primary cycle adsorption: introducing the filtered supernatant into treatment equipment, adsorbing the filtered supernatant by using adsorption resin, and controlling the treatment equipment to perform internal circulation so that the filtered supernatant is repeatedly subjected to primary adsorption circulation treatment for 15-25 min by using the adsorption resin;
s4, reduced pressure distillation: sealing the treatment equipment, carrying out reduced pressure treatment on the treatment equipment, reducing the pressure in the treatment equipment to 1.33-2.60 kPa, controlling the heating temperature of the treatment equipment to be 30-40 ℃, and carrying out reduced pressure distillation on the wastewater in the treatment equipment until the distilled part is not increased any more;
s5, secondary cycle adsorption: after the reduced pressure distillation is finished, continuously performing in vivo circulation on the residual waste liquid in the treatment equipment, and performing secondary adsorption circulation treatment for 15-25 min by using adsorption resin;
s6, boosting: controlling the interior of the processing equipment to carry out boosting treatment, so that the interior of the processing equipment is recovered to a normal pressure state, and in the boosting process, keeping the temperature inside the processing equipment stable, and reducing temperature change;
s7, feed liquid recovery: and finally, residual liquid in the treatment equipment is discharged and recycled, so that the treatment equipment is convenient to recycle.
2. The process for recovering the nitric acid from the nitrified wastewater as claimed in claim 1, wherein a filter medium in the filtering device used in the S2 is a molecular sieve, and the filling thickness of the molecular sieve is 15-25 cm.
3. The process for recovering nitric acid from nitrified waste water of claim 1, wherein the adsorbent resin is a macroporous adsorbent resin, and the basic raw materials are styrene and propionate.
4. The process for recovering nitric acid from nitrifying wastewater according to claim 3, wherein the adsorption resin is prepared from the following raw materials in percentage by mass:
10-15 parts of styrene;
12-16 parts of propionate;
1-3 parts of styrene;
0.5-0.9 part of toluene;
0.3-0.8 part of dimethylbenzene.
5. The process for recovering nitric acid from nitrifying wastewater according to claim 4, wherein the preparation process of the adsorption resin comprises the following steps: styrene and acrylic acid were added to a 0.5% gelatin solution, and styrene was added thereto, and toluene and xylene were added thereto to form a pore skeleton structure by mutual crosslinking.
6. The process for recovering the nitric acid from the nitrified wastewater according to claim 1, wherein the process for recovering the nitric acid from the nitrified wastewater is based on a recovery device, the device comprises a recovery tank (1), two sets of separation nets (2), an adsorption resin (3), a communicating pipe (4), a circulating pump (5), a separation barrel (6), a first transmission pipe (7), a U-shaped filter barrel (8), a second transmission pipe (9), a liquid suction pump (10), a sealing cover (11), a plurality of sets of legs (12) and a liquid discharge pipe (13), a recovery cavity is arranged in the recovery tank (1), a cleaning port is communicated with the top of the recovery tank (1), the cleaning port is communicated with the recovery cavity, the sealing cover (11) is arranged on the top of the recovery tank (1), two sets of fixing holes and ventilation holes are arranged on the sealing cover (11), and a vacuum suction pipe (14) and a discharge pipe (15) are respectively arranged on the inner walls of the two sets of fixing holes, switch valves (16) are arranged on the vacuum pumping pipe (14) and the discharge pipe (15), the two groups of partition nets (2) are transversely arranged in the recovery box (1), the adsorption resin (3) is positioned between the two groups of partition nets (2), two ends of the communicating pipe (4) are respectively communicated with the upper half area and the lower half area of the recovery box (1), the circulating pump (5) is arranged on the communicating pipe (4), a separation cavity is arranged in the separation barrel (6), a liquid filling port is communicated with the top of the separation barrel (6), the input end of the first transmission pipe (7) penetrates through the side wall of the separation barrel (6) and extends into the separation barrel (6), a liquid pumping pump (10) is arranged on the first transmission pipe (7), a filter cavity is arranged in the U-shaped filter barrel (8), the output end of the first transmission pipe (7) is communicated with the U-shaped filter barrel (8), two ends of the second transmission pipe (9) are respectively communicated with the U-shaped filter barrel (8) and the recovery box (1), and a control valve (17) is arranged on the second transmission pipe (9), the U-shaped filter barrel (8) is filled with a molecular sieve (18), the plurality of groups of support legs (12) are all arranged at the bottom of the recovery box (1), the liquid discharge pipe (13) is communicated with the bottom of the recovery box (1), a discharge valve (19) is arranged on the liquid discharge pipe (13), and a ventilation valve (20) is arranged at the ventilation hole.
7. The process for recovering nitric acid from nitrified wastewater according to claim 6, wherein the recovery equipment further comprises a plurality of groups of support rods (21) and a plurality of groups of support blocks (22), both ends of the plurality of groups of support rods (21) are respectively connected with the plurality of groups of support blocks (22) and the bottom of the recovery box (1), and the plurality of groups of support blocks (22) are all in contact with the bottom of the partition net (2) on the lower side.
8. The process for recovering nitric acid from nitrified waste water according to claim 7, wherein a temperature control layer (23) is wrapped on the outer wall of the recovery device.
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