CN111559737A - Method for continuously extracting nitration waste acid - Google Patents
Method for continuously extracting nitration waste acid Download PDFInfo
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- CN111559737A CN111559737A CN202010458070.7A CN202010458070A CN111559737A CN 111559737 A CN111559737 A CN 111559737A CN 202010458070 A CN202010458070 A CN 202010458070A CN 111559737 A CN111559737 A CN 111559737A
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- extractor
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- chlorobenzene
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- 239000002253 acid Substances 0.000 title claims abstract description 99
- 239000002699 waste material Substances 0.000 title claims abstract description 93
- 238000000034 method Methods 0.000 title claims abstract description 51
- 238000006396 nitration reaction Methods 0.000 title claims abstract description 31
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims abstract description 72
- 239000012071 phase Substances 0.000 claims abstract description 70
- 239000000463 material Substances 0.000 claims abstract description 44
- 238000000605 extraction Methods 0.000 claims abstract description 43
- 239000012074 organic phase Substances 0.000 claims abstract description 42
- 238000004519 manufacturing process Methods 0.000 claims abstract description 24
- 238000000926 separation method Methods 0.000 claims abstract description 16
- 239000002994 raw material Substances 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 238000010306 acid treatment Methods 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims description 98
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 18
- 150000002823 nitrates Chemical class 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- FHWRLVLDNKNYGD-UHFFFAOYSA-N nitrobenzene;hydrochloride Chemical compound Cl.[O-][N+](=O)C1=CC=CC=C1 FHWRLVLDNKNYGD-UHFFFAOYSA-N 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 14
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 14
- 238000006243 chemical reaction Methods 0.000 abstract description 9
- VYZAHLCBVHPDDF-UHFFFAOYSA-N Dinitrochlorobenzene Chemical compound [O-][N+](=O)C1=CC=C(Cl)C([N+]([O-])=O)=C1 VYZAHLCBVHPDDF-UHFFFAOYSA-N 0.000 description 7
- BFCFYVKQTRLZHA-UHFFFAOYSA-N 1-chloro-2-nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1Cl BFCFYVKQTRLZHA-UHFFFAOYSA-N 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000000630 rising effect Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000000802 nitrating effect Effects 0.000 description 2
- 150000004767 nitrides Chemical class 0.000 description 2
- 230000001546 nitrifying effect Effects 0.000 description 2
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000003908 quality control method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/94—Recovery from nitration acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0488—Flow sheets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D11/00—Solvent extraction
- B01D11/04—Solvent extraction of solutions which are liquid
- B01D11/0492—Applications, solvents used
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D17/00—Separation of liquids, not provided for elsewhere, e.g. by thermal diffusion
- B01D17/02—Separation of non-miscible liquids
- B01D17/0217—Separation of non-miscible liquids by centrifugal force
-
- C—CHEMISTRY; METALLURGY
- 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
- C02F1/26—Treatment of water, waste water, or sewage by extraction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/36—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the manufacture of organic compounds
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The invention discloses a method for continuously extracting nitration waste acid, which is characterized in that a plurality of extractors are installed in series, and a separator is arranged at the upper part of the extractor; the process from chlorobenzene addition to chlorobenzene outflow from the separator of the last extractor is an extraction continuously flowing through a plurality of extractors, and the process from waste acid addition from the last extractor to outflow from the first extractor is an extraction continuously flowing through a plurality of extractors; the mixture is lifted to a separator through a lifter, the separator separates an organic phase and an inorganic phase of the material, and after separation, the organic phase flows into the next extractor; the inorganic phase flows into the last extractor, and the inorganic phase of the separator of the first extractor enters the waste acid treatment device. The reaction process of the invention is continuously carried out, and the operation is continuous and automatic, thereby reducing the labor intensity and enlarging the production capacity; in the method, chlorobenzene is used for extracting the nitrated substance and the nitric acid in the acid phase, and the nitrated substance is recovered, so that the consumption of raw materials is reduced, and the utilization rate of the nitric acid is improved.
Description
Technical Field
The invention relates to a technology for treating and utilizing nitrified waste acid, in particular to a method for continuously extracting nitrified waste acid.
Background
Nitration reactions are important reactions for the production of dyes, pharmaceuticals and certain explosives and are now widely used in the chemical industry. The nitration is carried out by taking mixed acid (mixture of concentrated nitric acid and concentrated sulfuric acid) as nitrating agent, wherein the sulfuric acid plays a role of catalyst and does not participate in the reaction. Waste acid is generated in the reaction, and the waste acid generated in the reaction needs to be extracted and concentrated to 90-95% sulfuric acid for production or mixed acid preparation, so that the purpose of recovering sulfuric acid is achieved. Extraction is an essential process in nitration production.
The prior nitration waste acid extraction in China adopts discontinuous production, and the discontinuous process production generally exists:
firstly, each operation action is periodically changed, the operation is troublesome, the automatic control is difficult to be carried out, and the intermittent waiting time is usually existed between two periods, so the utilization rate of equipment is low;
secondly, the condition variation of each operation is large, and the product quality fluctuation is large;
the production capacity is low, the labor intensity is high, the cost is high, and the safety and the product quality can not be ensured.
In view of the above-mentioned defects, scientific and technical personnel have conducted a lot of research and published a lot of literature attempts to solve the problems, but these methods all have the defects of low production capacity, unstable quality control, no guarantee of safety, difficulty in realizing industrial large-scale continuous production, and the like.
Disclosure of Invention
The invention aims to provide a method for continuously extracting nitration waste acid, which solves the technical problem of sulfuric acid recycling in the continuous extraction process of nitration waste acid in 2,4 dinitrochlorobenzene prepared by nitration of nitrochlorobenzene; the method is a technological means which is suitable for large-scale industrial production, can ensure the safety and stability of production and the quality of products, reduces the loss of raw materials and the generation of three wastes, improves the production efficiency, reduces the energy consumption and ensures the production safety and the product quality.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for continuously extracting nitrified waste acid is characterized in that the nitrified waste acid is continuously extracted to prepare sulfuric acid for recycling; the method comprises the following steps:
the method uses a plurality of extractors to be installed in series, and the extractors comprise: the device comprises a cleaning opening, a coil pipe, an extractor, a stirrer, a lifter, a separator, a rack and a motor, wherein the separator is arranged at the upper part of the extractor and is higher than the extractor; chlorobenzene is added into an extractor of a first extractor, waste acid is added into an extractor of a last extractor, the process from chlorobenzene addition to chlorobenzene outflow from a separator of the last extractor is extraction continuously flowing through a plurality of extractors, and the process from waste acid addition from the last extractor to the outflow from the first extractor is extraction continuously flowing through the plurality of extractors.
The method comprises the following steps that materials of chlorobenzene and nitration waste acid mixtures in an extractor are lifted into a separator through the lifter, the separator separates organic phases and inorganic phases of the materials, the organic phases flow into the next extractor after separation, and the organic phase of the separator of the last extractor enters a transfer tank; the inorganic phase of the separator of the last extractor flows into the last extractor, and the inorganic phase of the separator of the first extractor enters the waste acid treatment device. Thus realizing continuous extraction and reducing consumption.
Specifically, the motor is arranged at the top of the extraction machine and drives the stirring shaft through the frame.
Specifically, the clean discharge port is positioned at the lower part of the extractor; the coil is arranged in the extractor and is used for introducing a heating medium to heat; the stirrer is arranged in the middle of the extractor, the stirring shaft is arranged in the middle of the stirrer, the stirring shaft penetrates through the lifter and the separator, and the stirring shaft is driven by a motor arranged at the top of the extractor.
Specifically, the extractor still be provided with the journal stirrup, the journal stirrup sets up in the outside of extractor, fixes the extractor through the journal stirrup.
Specifically, the extractor is further provided with a filler seal, and the filler seal is arranged at the joint of the stirring shaft and the upper end enclosure of the extractor.
More specifically, the organic phase flows into a transfer tank for storage and then is used as a raw material in production.
Thus, the organic phase, namely chlorobenzene phase containing the nitrated compound, generated in the whole extraction device and the inorganic phase, namely the nitrified waste acid phase form reverse flow, and the waste acid of the low-concentration nitric acid is treated in the next step.
Specifically, the separator separates the nitrates from the extracted waste acid, specifically: after extraction, the nitrobenzene phase containing the nitrated compounds and the nitrated spent acid phase are separated dynamically by centrifugation, due to their different densities. The nitrated compound is dissolved in chlorobenzene, the waste acid and the nitrated compound-containing chlorobenzene are insoluble and separated, and the density of the waste acid and the nitrated compound-containing chlorobenzene is different. Therefore, when the separator drum rotates under the centrifugal rotation state of the waste acid phase with high density, namely the inorganic phase, the waste acid phase clings to the drum to rotate, and then enters the heavy liquid receiving tank; under the centrifugal rotation state of the low-density nitrobenzene-chloride phase containing the nitrates, when the separator drum rotates, the nitrates rotate at the inner side of the waste acid and enter the light liquid receiving tank, so that the nitrates can be separated.
Specifically, the extraction temperature of the extractor is 40-95 ℃, the preferred extraction temperature is 50-80 ℃, and the more preferred extraction temperature is 60-75 ℃.
Specifically, the number of the extractors can be 2 to 6. The specific amount is designed according to the output of the nitrified waste acid.
More specifically, chlorobenzene enters the extractor from the upper part of the first extractor through a pipeline, and waste acid enters the extractor from the upper part of the last extractor through a pipeline. .
More specifically, the organic phase flows into the next extractor until flowing into a transfer tank, and is used as a raw material in production after being stored; the inorganic phase flows into the previous extractor until the inorganic phase flows into a waste acid treatment device.
The waste nitrifying acid is produced by nitrifying mononitrochlorobenzene to obtain 2, 4-dinitrochlorobenzene, and the reaction materials are mononitrochlorobenzene and mixed acid which is used as nitrating agent and consists of mixed acid
Sulfuric acid of (D),
Nitric acid of,
The sum of all the components in the mixed acid is 100 percent. Specifically, the inorganic phase obtained by the reaction in the discontinuous or semi-continuous production of 2,4 dinitrochlorobenzene prepared by nitration of mononitrochlorobenzene can be obtained according to the Chinese patent process of the grant publication No. CN 102070457B.
Dinitrochlorobenzene is mainly used as an intermediate, a polymerization assistant and the like for preparing dyes, medicines and pesticides, and has a molecular formula C6H3Cl(NO2)2It has six isomers, and dinitrochlorobenzene with 2, 4-dinitrochlorobenzene structure is required to be produced.
The nitration of mononitrochlorobenzene to dinitrochlorobenzene is of the formula:
further specifically, the mass composition of the nitrified waste acid is as follows: 2.5-5.0% of nitric acid, 60-80% of sulfuric acid, 0.3-1% of nitride, 14-37.2% of water and the balance of inevitable by-products and impurities.
The nitrified waste acid is extracted by chlorobenzene and then comprises the following components in percentage by mass: the content of nitric acid is less than 0.25 percent, the content of sulfuric acid is 60 to 80 percent, the content of nitride is less than 0.1 percent, the content of water is 19.65 to 39.65 percent, and the balance is inevitable by-products and impurities.
The invention provides a method for continuously extracting nitration waste acid, which has the further specific technical scheme that:
the specific method for enabling the mixture of the nitration waste acid phase and the chlorobenzene phase to enter the high-liquid-level separator from the extractor comprises the following steps: the mixed phase in the extractor is lifted to the separator for separation through a lifter, the lifter is positioned in the center of the extractor, the lifter is a funnel-type cylinder body arranged on the stirring shaft and rotates along with the rotation of the stirring shaft, the funnel-type cylinder body comprises a material inlet at the lower part and a material outlet at the upper part, and the outer diameter of the material inlet is smaller than that of the material outlet; a rib plate is welded on the inner wall of the cylinder body; specifically, the rib plates are a plurality of rib plates which are distributed uniformly, and the rib plates penetrate through the inner wall of the whole cylinder body; the inner rib plate of the lifter has the function of synchronizing the rotation of the liquid and the lifter so as to obtain the centrifugal force for enabling the material to move upwards along the inner wall of the cylinder; the material inlet of the lifter is inserted into the material in the extractor, and when the lifter rotates, centrifugal force generated by rotation forms upward component force to force liquid to flow so as to achieve the lifting purpose.
Specifically, the lifter is a conveying tool in the device, and lifts the mixed phase in the extractor into the separator for separation. After the lifter is adopted, a plurality of devices can be arranged on one plane; the action principle of the lifter is that centrifugal force generated by rotation forms upward component force to force liquid to flow so as to achieve the purpose of lifting. Because the lifter is provided with the rib plates in the lifter when rotating, the liquid is ensured to obtain the angular velocity to generate an ascending force when rotating, and the following formula can be obtained by the Bernoulli equation
Namely, equation (1). The formula H1 is the rising force or the rising height, the unit is meter, n is the rotating speed r.p.m, R0Is the radius of the upper opening of the lifter, and the unit is meter, r0The radius of the shaft sleeve of the lifter is measured in meters. Critical rotation speed of：H2For the actual height of the liquid, in meters, when H1>H2When the liquid is lifted, namely the lifting force is larger than the actual liquid lifting height, the liquid is lifted. Therefore, it is not only easy to use
When in use
When n is greater than n1For this purpose, the critical rotational speed of the lift, i.e. the rotational speed of the lift, must be greater than this for the lift to be lifted. H2See figure 4.
More specifically, the heavy liquid receiving tank of the separator is connected with a pipeline communicated with the extractor of the previous extractor and used as a heavy liquid circulating channel, and the inorganic phase, namely the waste acid, can be returned to the extractor of the previous extractor, so that the inorganic phase and the organic phase in the extractor keep the required proportion; and the inorganic phase material of the third separator flows to the second extraction machine, the inorganic phase material of the second extraction machine separator flows to the first extraction machine, and the rest is done in the same way until the inorganic phase treated by the first extraction machine separator enters a waste acid concentration device, and the concentrated inorganic phase is used for preparing mixed acid in nitration production. Through separation, the discharge of three wastes during waste acid concentration can be reduced, the waste acid concentration efficiency is improved, the organic matter recycling in the nitrified waste acid is improved, and the product consumption is reduced.
More specifically, the light liquid receiving tank of the separator is connected with a pipeline communicated with an extractor of the next extractor, and is used as a light liquid circulating channel, so that the organic phase can be returned to the extractor of the next extractor, and the required ratio of the inorganic phase to the organic phase in the extractor is kept; and the organic phase material of the first separator flows to a second extractor, the organic phase material of the second extractor separator flows to a third extractor, and the like is carried out until the organic phase processed by the last extractor separator enters a transfer tank, and the organic phase is stored to reach a certain amount and then used for preparing raw materials during nitration production.
More specifically, the heavy liquid receiving tank is provided with a heavy liquid outlet which is connected with the heavy liquid inlet of the last extraction machine through a pipeline; the light liquid receiving tank is provided with a light liquid outlet, and the light liquid outlet is connected to a light liquid inlet of the light liquid extractor through a pipeline.
More specifically, the rotary drum is of a cylinder structure, the lower part of the cylinder is connected with a discharge hole at the upper end of the lifter, a heavy liquid outlet and a light liquid outlet are arranged at the upper end of the cylinder, the heavy liquid outlet is arranged at a position close to the wall of the cylinder, and the light liquid outlet is arranged at a position close to the center of the cylinder.
For the present application, the heavy liquid is an inorganic phase, i.e. a spent acid phase; the light liquid is chlorobenzene phase, i.e. organic phase.
The separator aims to separate waste acid from organic matters, and a heavy liquid receiving tank and a light liquid receiving tank are arranged at an organic matter and waste acid outlet in the separator.
The centrifugal separation is dynamic liquid separation equipment, and liquid components with different densities are separated under the action of centrifugal force under the rotating condition of the equipment; the waste acid and the nitrated compound in the separator are subjected to different centrifugal forces due to different densities, so that the waste acid and the nitrated compound are separated. Because the density of the waste acid is high, when the rotary drum of the separator rotates, the waste acid is tightly attached to the rotary drum to rotate, and then enters the heavy liquid receiving tank; and the density of the nitrified substance is small, and when the rotary drum of the separator rotates, the nitrified substance rotates at the inner side of the waste acid and enters the light liquid receiving tank.
In particular, see schematic diagrams of the separation of the free surfaces within the lifter and dynamic separator drum.
The invention provides a method for continuously extracting nitrified waste acid, which is characterized in that chlorobenzene is added into an extractor to extract nitric acid in the nitrified waste acid into a chlorobenzene phase, namely an organic phase, so that the content of the nitric acid in the waste acid is reduced, and the content of the nitric acid in the waste acid can be controlled to be below 0.25%; meanwhile, suspended nitrates and partially dissolved nitrates in the chlorobenzene extraction waste acid are used, and the nitrates in the nitration waste acid are controlled to be below 0.1%, so that excessive impurities are avoided and three wastes are reduced during sulfuric acid concentration production.
After the materials are continuously and dynamically separated from the separator of the first extractor, separating out the organic phase in the extracted waste acid, and enabling the separated organic phase to enter the extractor of the second extractor through an inlet; the steps are continued until the liquid enters the extractor of the last extractor; the chlorobenzene, namely the organic phase, enters a first extractor, and continuously flows into a storage tank for producing raw materials through nitration reaction after flowing out of the last extractor;
after the materials are continuously and dynamically separated from the separator of the last extractor, separating out the organic phase from the extracted waste acid, and allowing the separated inorganic phase to flow into the extractor of the previous extractor, and continuing the process until the inorganic phase enters the extractor of the first extractor; the separated waste acid phase, namely an inorganic phase, enters a waste acid treatment device;
after the inorganic phase enters the waste acid treatment device, the inorganic phase can be separated again or concentrated to further improve the purity of the nitrified waste acid, reduce the pressure for the subsequent waste acid concentration process and reduce the discharge of three wastes.
The invention provides a method for continuously extracting nitration waste acid, and the further specific technical scheme can also be as follows: the extraction residence time of the mixed solution containing the nitrified waste acid and the chlorobenzene in each extractor is averagely 15-60 minutes; the organic phase material of the separator flows out of the separator and is stored to reach a certain amount, and the organic phase material can be used as raw material in the production of nitre after being processed. The plurality of extractors at least comprise a first extractor and a last extractor, and when the plurality of extractors comprise two extractors, the second extractor is the last extractor.
The contents and the proportions in the technical scheme of the patent application are mass contents and proportions if not specifically stated.
The invention provides a method for continuously extracting nitration waste acid, which has the beneficial effects that: the reaction process is continuously carried out, and the continuous automatic operation reduces the labor intensity and enlarges the production capacity; in the method, chlorobenzene is used for extracting the nitrated substance and the nitric acid in the acid phase, the nitrated substance in the acid phase is recovered, the consumption of raw materials is reduced, and the utilization rate of the nitric acid is improved.
It has the following characteristics:
(1) the technological parameters are constant and basically not changed along with time during steady-state operation, so that the reaction can be carried out under favorable conditions, and the extraction efficiency and the sulfuric acid quality are favorably improved.
(2) Because the process condition change is small, the operation is convenient for workers, the safe production is facilitated, the automation and the remote control are easy to realize, and the quality is relatively stable.
(3) Except for maintenance and fault, the equipment is in a continuous operation state, so the utilization rate of the equipment is high.
(4) The continuous extraction has high production intensity, unit volume and large production capacity in unit time.
(5) Due to the arrangement of the separator, after the extraction mixture is separated, the organic phase material and the inorganic phase material respectively enter different extraction machines, so that the extraction is more pertinent, the materials in the whole extraction process flow as required, the processes of ineffective extraction, inefficient extraction and repeated extraction caused by the circular flow of part of the materials in the material flow process are avoided, and the extraction effect is better;
(6) because the stirring shaft is used for providing power required by lifting and separating, and a power device is not required to be arranged in the separator and the lifter independently, the energy and equipment investment are saved.
Drawings
FIG. 1 is a schematic diagram of a continuous extraction method of nitrified waste acid.
FIG. 2 is a schematic view of an extractor.
Wherein: 1 is a discharge port, 2 is a coil pipe, 3 is an extractor barrel, 4 is a stirrer, 5 is a stirring shaft, 6 is an organic phase feed inlet lower section, 7 is an inorganic phase feed inlet lower section, 8 is a support lug, 9 is a lifter, 10 is an extractor flange, 11 is a separator barrel, 12 is sealing filler, 13 is a frame, 14 is a light liquid outlet, 15 is an inorganic phase inlet, 16 is a heavy liquid outlet, and 17 is an organic phase inlet.
Fig. 3 is a combination of an extractor, a riser, and a separator. Wherein: 21 is an extractor, 22 is a lower opening of the lifter, 9 is the lifter, 24 is a material liquid level indication in the extractor, and 25 is a separator.
FIG. 4 is a schematic illustration of the lifter and the separation of the free surface within the dynamic separator drum. Wherein: 3 is an extractor cylinder, 9 is a lifter, 31 is a separator drum, 5 is a stirring shaft, 13 is a heavy liquid receiving tank, 24 is an unseparated organic phase and inorganic phase mixed material, 32 is the flow direction of the unseparated organic phase and inorganic phase mixed material, 33 is the light liquid separation aggregation and flow direction, and 34 is the light liquid receiving tank.
Fig. 5 is a schematic diagram of the mixed liquor in the centrifugal separator.
In FIG. 5, the mixed liquid is dynamically separated at a flow rate qVEnters a dynamic separator and reaches a plane B from a plane A at an average flow velocity upsilon, AB is L, and the separator rotates around an axis at an angular velocity omega.
The respective symbols in fig. 5 mean: upsilon is the average flow velocity, qV is the flow of the dynamically separated mixed liquor, omega is the angular velocity of the separator, RHIs the heavy liquid outlet radius, RLIs the light liquid outlet radius, rHIs the radius of the liquid level at the heavy liquid outlet, rLIs the radius of the liquid level at the light liquid outlet, RDThe radius of the liquid surface of heavy liquid and light liquid separation is shown, R is the radius of a drum of the separator, upsilonteThe speed of the mixed liquid in the centrifugal direction is shown as A, the lower liquid level of the separator and the upper liquid level of the separator.
FIG. 6 is a schematic flow diagram of the nitration reaction mass.
FIG. 7 is a schematic material flow diagram of a continuous extraction process for nitrated spent acid including three extractors.
Detailed Description
The present patent application is further illustrated below with reference to examples, in which various contents and ratios are, for example, mass contents and ratios without specific description.
Example 1
According to the method described in this patent application, the extractors 1, 2, 3 are provided with separating means. The inorganic phase control conditions and the organic phase average residence time for each extractor are shown in Table 1 below. The adding proportion of the total amount of chlorobenzene, the total amount of nitric acid and the total amount of sulfuric acid is that chlorobenzene: total amount of nitric acid: total amount of sulfuric acid 1: 1.2: 1.5.
TABLE 1
Example 2
According to the method described in this patent application, 3 extractors are installed in series, each equipment is made of 316L stainless steel, the extractor includes: the device comprises a cleaning opening 1, a coil 2, an extractor 21, a stirrer 4, a lifter 9, a separator 25, a frame and a motor, wherein the separator 25 is arranged at the upper part of the extractor 21 and is higher than the extractor 21; chlorobenzene is fed into the extractor 21 of the first extractor, spent acid is fed into the extractor 21 of the last extractor, the process from the feeding of chlorobenzene to the outflow of chlorobenzene from the separator 25 of the last extractor is an extraction continuously flowing through a plurality of extractors, and the process from the feeding of spent acid from the last extractor to the outflow of spent acid from the first extractor is an extraction continuously flowing through a plurality of extractors.
The separator 25 is arranged at the center of the extractor, and the separator 25 comprises a rotary drum 31, a heavy liquid receiving tank 13 and a light liquid receiving tank 34; the rotary drum 31 is arranged on the stirring shaft 5 and rotates along with the rotation of the stirring shaft 5, the material outlet of the lifter 9 is connected with the rotary drum, and the lifted material enters the rotary drum 31 of the separator 25; the heavy liquid receiving tank 13 is arranged in the separator 25 and is higher than the light liquid receiving tank 34, the inlet of the heavy liquid receiving tank corresponds to the heavy liquid outlet 16 of the rotary drum 31 and is used for receiving materials thrown out by centrifugal force when the rotary drum 31 rotates, and the heavy liquid receiving tank 13 is connected with a pipeline communicated with the extractor 21 of the previous extractor and used as a circulating channel of heavy liquid; the light liquid receiving groove 34 is arranged in the separator 25 and is lower than the heavy liquid receiving groove 13, and the inlet of the light liquid receiving groove corresponds to the light liquid outlet 14 of the rotary drum 31 and is used for receiving materials thrown out by centrifugal force when the rotary drum 31 rotates; the light liquid receiving tank 34 is connected to a pipe leading to the extractor 21 of the next extractor as a circulation passage for the light liquid.
Example 3
The lifting device 9 is a conveying tool in the device, and lifts the mixed phase in the extractor 21 to the separator 25 for separation. After the lifter 9 is adopted, a plurality of devices can be arranged on one plane; the lifter 9 works on the principle that centrifugal force generated by rotation forms an upward component force to force liquid to flow so as to achieve the purpose of lifting. Because the lifter 9 rotates due to the rib plate in the lifter, liquid is certainly obtained during rotationThe angular velocity is obtained to generate a lifting force, and the following formula can be obtained by the Bernoulli equation
Namely, equation (1). The formula H1 is the rising force or the rising height, the unit is meter, n is the rotating speed r.p.m, R0Is the radius of the upper opening of the lifter 9, and the unit is meter, r0The radius of the shaft sleeve of the lifter 9 is measured in meters. Critical rotation speed: h2 is the actual lifting height of liquid in meters, when H1>H2, i.e. the lifting force is greater than the actual liquid height to be lifted, the liquid is lifted up. Therefore, it is not only easy to use
When in use
When n is greater than n1For this purpose, the critical rotational speed of the lift 9, i.e. the rotational speed of the lift 9, must be greater than this for the lift to be able to be increased.
Claims (10)
1. A method for continuously extracting nitrified waste acid is characterized in that the nitrified waste acid is continuously extracted to prepare sulfuric acid for recycling; the method is characterized in that: the method uses a plurality of extractors to be installed in series, and the extractors comprise: the device comprises a cleaning opening, a coil pipe, an extractor, a stirrer, a lifter, a separator, a rack and a motor, wherein the separator is arranged at the upper part of the extractor and is higher than the extractor; chlorobenzene is added into an extractor of a first extractor, waste acid is added into an extractor of a last extractor, the process from chlorobenzene addition to chlorobenzene outflow from a separator of the last extractor is extraction continuously flowing through a plurality of extractors, and the process from waste acid addition from the last extractor to the outflow from the first extractor is extraction continuously flowing through the plurality of extractors;
the method comprises the following steps that materials of chlorobenzene and nitration waste acid mixtures in an extractor are lifted into a separator through the lifter, the separator separates organic phases and inorganic phases of the materials, the organic phases flow into the next extractor after separation, and the organic phase of the separator of the last extractor enters a transfer tank; the inorganic phase of the separator of the last extractor flows into the last extractor, and the inorganic phase of the separator of the first extractor enters a waste acid treatment device;
the motor is arranged at the top of the extractor and drives the stirring shaft through the frame; the emptying port is positioned at the lower part of the extractor; the coil is arranged in the extractor and is used for introducing a heating medium to heat; the stirrer is arranged in the middle of the extractor, the stirring shaft is arranged in the middle of the stirrer, the stirring shaft penetrates through the lifter and the separator, and the stirring shaft is driven by a motor arranged at the top of the extractor.
2. The method for continuously extracting nitration waste acid according to claim 1, which is characterized by comprising the following steps: the separator separates the nitrated compound in the extracted waste acid, and specifically comprises the following steps: after extraction, dynamic separation is carried out by a centrifugal method due to different densities of a chlorobenzene phase containing the nitrated compound and a nitration waste acid phase; the nitrated substance is in a dissolved state in chlorobenzene, the waste acid and the nitrated substance-containing chlorobenzene are in an insoluble separation state, and the densities of the waste acid and the nitrated substance-containing chlorobenzene are different; therefore, when the separator drum rotates under the centrifugal rotation state of the waste acid phase with high density, namely the inorganic phase, the waste acid phase clings to the drum to rotate, and then enters the heavy liquid receiving tank; under the centrifugal rotation state of the low-density nitrobenzene-chloride phase containing the nitrates, when the separator drum rotates, the nitrates rotate at the inner side of the waste acid and enter the light liquid receiving tank, so that the nitrates can be separated.
3. The method for continuously extracting nitration waste acid according to claim 1, which is characterized by comprising the following steps: the specific method for feeding the mixture of the nitration waste acid phase and the chlorobenzene phase from the extractor into the high-liquid-level separator comprises the following steps: the mixed phase in the extractor is lifted to the separator for separation through a lifter, the lifter is positioned in the center of the extractor, the lifter is a funnel-type cylinder body arranged on the stirring shaft and rotates along with the rotation of the stirring shaft, the funnel-type cylinder body comprises a material inlet at the lower part and a material outlet at the upper part, and the outer diameter of the material inlet is smaller than that of the material outlet; a rib plate is welded on the inner wall of the cylinder body; the material inlet of the lifter is inserted into the material in the extractor, and when the lifter rotates, centrifugal force generated by rotation forms upward component force to force liquid to flow so as to achieve the lifting purpose.
4. The method for continuously extracting the nitrified waste acid as claimed in claim 2, which is characterized in that: the heavy liquid receiving tank of the separator is connected with a pipeline communicated with the extractor of the previous extractor and used as a circulating channel of heavy liquid, and an inorganic phase, namely waste acid, can be returned to the extractor of the previous extractor, so that the inorganic phase and the organic phase in the extractor keep the required proportion; and the inorganic phase material of the third separator flows to the second extraction machine, the inorganic phase material of the second extraction machine separator flows to the first extraction machine, and the rest is done in the same way until the inorganic phase treated by the first extraction machine separator enters a waste acid concentration device, and the concentrated inorganic phase is used for preparing mixed acid in nitration production.
5. The method for continuously extracting the nitrified waste acid as claimed in claim 2, which is characterized in that: the light liquid receiving tank of the separator is connected with a pipeline communicated with an extractor of the next extractor and used as a light liquid circulating channel, and an organic phase can be returned to the extractor of the next extractor, so that the inorganic phase and the organic phase in the extractor keep the required proportion; and the organic phase material of the first separator flows to a second extractor, the organic phase material of the second extractor separator flows to a third extractor, and the like is carried out until the organic phase processed by the last extractor separator enters a transfer tank, and the organic phase is stored to reach a certain amount and then used for preparing raw materials during nitration production.
6. The method for continuously extracting the nitrified waste acid as claimed in claim 2, which is characterized in that: the heavy liquid receiving tank is provided with a heavy liquid outlet which is connected with the heavy liquid inlet of the last extraction machine through a pipeline; the light liquid receiving tank is provided with a light liquid outlet, and the light liquid outlet is connected to a light liquid inlet of the light liquid extractor through a pipeline.
7. The method for continuously extracting the nitrified waste acid as claimed in claim 2, which is characterized in that: the drum is a cylinder structure, the lower part of the cylinder is connected with a discharge hole at the upper end of the lifter, the upper end of the cylinder is provided with a heavy liquid outlet and a light liquid outlet, the heavy liquid outlet is arranged at a position close to the wall of the cylinder, and the light liquid outlet is arranged at a position close to the center of the cylinder.
8. The method for continuously extracting nitration waste acid according to claim 1, which is characterized by comprising the following steps: chlorobenzene enters the extractor from the upper part of the first extractor through a pipeline, and waste acid enters the extractor from the upper part of the last extractor through a pipeline.
9. The method for continuously extracting nitration waste acid according to claim 1, which is characterized by comprising the following steps: the organic phase flows into the next extractor until the organic phase flows into a transfer tank, and the organic phase is stored and then used as a raw material in production; the inorganic phase flows into the previous extractor until the inorganic phase flows into a waste acid treatment device.
10. The method for continuously extracting the nitrified waste acid as claimed in claim 2, which is characterized in that: the drum is a cylinder structure, the lower part of the cylinder is connected with a discharge hole at the upper end of the lifter, the upper end of the cylinder is provided with a heavy liquid outlet and a light liquid outlet, the heavy liquid outlet is arranged at a position close to the wall of the cylinder, and the light liquid outlet is arranged at a position close to the center of the cylinder.
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| CN112679362A (en) * | 2020-12-30 | 2021-04-20 | 东营安诺其纺织材料有限公司 | Extraction system and process for preparing 2, 4-dinitrochlorobenzene to generate acid phase |
| CN112707823A (en) * | 2020-12-30 | 2021-04-27 | 东营安诺其纺织材料有限公司 | Green, safe, efficient and continuous 2, 4-dinitrochlorobenzene production system and method |
| CN113582146A (en) * | 2021-08-26 | 2021-11-02 | 浙江迪邦化工有限公司 | Method for producing nitrosyl sulfuric acid by using chlorobenzene and nitration waste acid |
| CN113651698A (en) * | 2021-08-17 | 2021-11-16 | 西安万德能源化学股份有限公司 | Treatment method for improving stability of waste acid obtained after synthesis of isopropyl nitrate |
| CN115028533A (en) * | 2022-06-28 | 2022-09-09 | 石家庄腾辉化工有限公司 | Method for preparing 2, 4-dinitrochlorobenzene by continuous nitration |
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| CN113651698A (en) * | 2021-08-17 | 2021-11-16 | 西安万德能源化学股份有限公司 | Treatment method for improving stability of waste acid obtained after synthesis of isopropyl nitrate |
| CN113651698B (en) * | 2021-08-17 | 2024-01-12 | 西安万德能源化学股份有限公司 | Treatment method for improving stability of waste acid after isopropyl nitrate synthesis |
| CN113582146A (en) * | 2021-08-26 | 2021-11-02 | 浙江迪邦化工有限公司 | Method for producing nitrosyl sulfuric acid by using chlorobenzene and nitration waste acid |
| CN115028533A (en) * | 2022-06-28 | 2022-09-09 | 石家庄腾辉化工有限公司 | Method for preparing 2, 4-dinitrochlorobenzene by continuous nitration |
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Application publication date: 20200821 |