CN111807593B - Salt-containing organic wastewater treatment and utilization integrated device and process for para-aramid solvent working section - Google Patents
Salt-containing organic wastewater treatment and utilization integrated device and process for para-aramid solvent working section Download PDFInfo
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- 150000003839 salts Chemical class 0.000 title claims abstract description 71
- 239000002904 solvent Substances 0.000 title claims abstract description 45
- 229920003235 aromatic polyamide Polymers 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 36
- 238000004065 wastewater treatment Methods 0.000 title abstract description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 115
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 84
- 229910001868 water Inorganic materials 0.000 claims abstract description 84
- 239000002351 wastewater Substances 0.000 claims abstract description 69
- 239000011780 sodium chloride Substances 0.000 claims abstract description 57
- 238000000605 extraction Methods 0.000 claims abstract description 31
- 239000012046 mixed solvent Substances 0.000 claims abstract description 29
- 238000003860 storage Methods 0.000 claims abstract description 28
- 239000002131 composite material Substances 0.000 claims abstract description 26
- 238000011084 recovery Methods 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- 239000012452 mother liquor Substances 0.000 claims abstract description 18
- 230000003068 static effect Effects 0.000 claims abstract description 15
- 238000004064 recycling Methods 0.000 claims abstract description 12
- 239000013078 crystal Substances 0.000 claims description 20
- 239000000243 solution Substances 0.000 claims description 18
- 238000007380 fibre production Methods 0.000 claims description 14
- 238000004062 sedimentation Methods 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- 238000007599 discharging Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000010992 reflux Methods 0.000 claims description 7
- 239000011259 mixed solution Substances 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 4
- 238000009489 vacuum treatment Methods 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000012808 vapor phase Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 36
- 239000000835 fiber Substances 0.000 description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000006116 polymerization reaction Methods 0.000 description 6
- 239000002994 raw material Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 238000012946 outsourcing Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 125000001140 1,4-phenylene group Chemical group [H]C1=C([H])C([*:2])=C([H])C([H])=C1[*:1] 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 229910001200 Ferrotitanium Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229920006253 high performance fiber Polymers 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 229920003366 poly(p-phenylene terephthalamide) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- MHSKRLJMQQNJNC-UHFFFAOYSA-N terephthalamide Chemical compound NC(=O)C1=CC=C(C(N)=O)C=C1 MHSKRLJMQQNJNC-UHFFFAOYSA-N 0.000 description 1
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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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- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
-
- 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
- C02F2001/007—Processes including a sedimentation step
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
Abstract
The invention belongs to the technical field of organic wastewater treatment, and particularly relates to a recovery treatment device and a recovery treatment process of organic wastewater containing salt in a para-aramid production process. The salt-containing organic wastewater recycling device comprises a static mixer, an extraction tower, an evaporator, a settling chamber, a mixed solvent preparation tank, a water removal tower and a composite solvent storage tank which are connected in sequence; the inlet of the static mixer is respectively connected with a mother liquor conveying pipeline and CHCl 3 A delivery line; the upper outlet of the extraction tower is connected with the evaporator through an overflow pipeline, and the bottom outlet of the extraction tower is connected with CHCl 3 A discharge line; the bottom outlet of the evaporator is connected with a centrifugal machine through a pipeline, the outlet of the centrifugal machine is divided into two branches, one branch is connected with a NaCl discharge pipeline, and the other branch is connected with the inlet of the settling chamber; the top inlet of the mixed solvent preparation tank is respectively connected with a water conveying pipeline and CaCl 2 A solution feed line and an NMP feed line. The invention fundamentally solves the problem that the salt-containing organic wastewater in the para-aramid solvent working section is difficult to treat.
Description
Technical Field
The invention belongs to the technical field of organic wastewater treatment, and particularly relates to a recovery treatment device and a recovery treatment process of organic wastewater containing salt in a para-aramid production process.
Background
The poly-p-phenylene terephthamide (PPTA) fiber is a para-aramid fiber for short, is a high-performance fiber, has excellent performances of high strength, high modulus, high temperature resistance, acid and alkali resistance, light weight and the like, has the specific strength of 5-6 times of steel wires, the specific modulus of 2-3 times of steel wires or glass fibers, has the toughness of 2 times of the steel wires, and has the weight of only about 20% of the steel wires. Therefore, the method has wide application in the fields of civil use and national defense. Although the para-aramid fiber has excellent performance, the problem of three wastes generated during the production of the para-aramid fiber is also outstanding, and especially the treatment of the salt-containing organic wastewater generated in the solvent section of the para-aramid fiber is a difficult problem in the industry.
All links of the polymerization section of para-aramid fiber are collected to be called mother liquor, and the mother liquor has low concentration of CaCl 2 NaCl, NMP (N-methylpyrrolidone) and H 2 O. CHCl for para-aramid solvent working section 3 NMP in the mother liquor is extracted, the extracted NMP is recycled, and the rest saline solution becomes saline organic wastewater of a solvent section. Although the solvent section can effectively recover NMP, the recovery rate reaches 98 percent, NMP is very soluble in water, and the extracted salt-containing wastewater still inevitably contains a small amount of NMP. Therefore, the components in the organic wastewater containing salt are CaCl 2 、NaCl、H 2 O, NMP the salt content is generally 3.5-5% (by mass, all are below), caCl 2 The mass ratio of the NMP to NaCl is 4:1, and the NMP content is only 800-3000 PPM. The salt content and COD of the salt-containing organic wastewater in the para-aramid solvent working section are far beyond the normal discharge index, and the salt-containing organic wastewater cannot be discharged. In addition, the organic wastewater treatment device of the sewage treatment plant has the requirement on the chloride ion content, the biochemical treatment can be carried out only when the chloride ion content is generally less than 0.6%, and the chloride ion content of the wastewater recovered by the para-aramid solvent is far beyond the maximum value of the biochemical treatment standard, so that biochemical bacteria can be killed directly, and the organic matters can not be subjected to biochemical treatment, therefore, the salt-containing organic wastewater in the para-aramid solvent section can not be directly discharged, and can not be directly subjected to biochemical treatment.
Because para-aramid is an emerging industry, the treatment device and the treatment process of salt-containing organic wastewater in the solvent section of para-aramid are not mature. In addition, the salt-containing organic wastewater has complex components, great treatment difficulty and high treatment cost. The current environmental protection situation is increasingly severe, and the treatment of the organic wastewater containing salt becomes a key point for determining the death and the survival of the para-aramid fiber industry.
In the para-aramid production process, a composite solvent is required to be prepared for the polymerization working section, and CaCl is required to be prepared for the composite solvent 2 、H 2 O, NMP. CaCl of current industry 2 The raw materials inevitably contain NaCl, and are generally high-quality CaCl 2 The raw materials include NaCl, impurities and CaCl 2 If the mass ratio of NaCl to impurities is higher than 5%, the NaCl and the impurities are enriched at the bottom of the water removal tower, so that the heat transfer at the bottom of the water removal tower is reduced, the temperature control is distorted, and then an inferior solvent is generated, thereby adversely affecting the polymerization section; in addition, the salt enriched at the bottom of the tower needs to be cleaned regularly, and is generally cleaned once in 20-30 days, so that the running cost of enterprises can be greatly increased due to the starting and stopping cost, the process stability, the waste generation and treatment and the like. In the organic wastewater containing salt, except NaCl, three raw materials are all provided. If the wastewater is treated, most NaCl is removed, and the other three raw materials can be used for preparing the composite solvent, so that the cost of treating the wastewater can be reduced, useful components in the wastewater can be recycled, and the capital of outsourcing raw materials is reduced, so that the composite solvent is obtained in one step.
The use of soluble carbonates, e.g. Na, is described in Chinese patent publication No. CN111072053A 2 CO 3 、NaHCO 3 、K 2 CO 3 、KHCO 3 Any one or more of Ca in the wastewater 2+ Conversion to CaCO 3 Precipitating, and evaporating to obtain salt crystal. The invention uses soluble carbonate Na 2 CO 3 、NaHCO 3 After treatment, the salt solution has single component and only NaCl, the subsequent evaporation process is well controlled, but the amount of soluble carbonate to be added is large, so that the cost of wastewater treatment is greatly increased; if K is used 2 CO 3 、KHCO 3 The treatment, the salt solution components are NaCl and KCl, the cost of wastewater treatment can be greatly increased, and the salt solution evaporation process of the NaCl and KCl is more difficult to control, and in addition, the salt crystals are a mixture of two salts, and are not separated, so that the salt crystals can only be treated according to solid hazardous waste, and the cost is high, so that enterprises cannot accept the salt crystals.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention provides a recovery treatment device for organic wastewater containing salt in the production process of para-aramid fiber. The recovery and treatment device for the salt-containing organic wastewater fundamentally solves the problem that the salt-containing organic wastewater in the para-aramid solvent working section is difficult to treat.
The invention also provides a recovery treatment process of the organic wastewater containing salt in the para-aramid production process, after the process is adopted to treat the organic wastewater containing salt, the removal rate of NaCl in the organic wastewater is 84%, and CaCl in the organic wastewater is treated simultaneously 2 、H 2 O and trace NMP are prepared into a composite solvent for recycling.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
the recovery treatment device for the organic wastewater containing salt in the para-aramid fiber production process comprises a static mixer, an extraction tower, an evaporator, a settling chamber, a mixed solvent preparation tank, a water removal tower and a composite solvent storage tank which are connected in sequence;
the inlet of the static mixer is respectively connected with a mother liquor conveying pipeline and CHCl 3 A delivery line;
the upper outlet of the extraction tower is connected with the evaporator through an overflow pipeline, and the bottom outlet of the extraction tower is connected with CHCl 3 A discharge line;
the bottom outlet of the evaporator is connected with a centrifugal machine through a pipeline, the outlet of the centrifugal machine is divided into two branches, one branch is connected with a NaCl discharge pipeline, and the other branch is connected with the inlet of the settling chamber;
the top inlet of the mixed solvent preparation tank is respectively connected with a water conveying pipeline and CaCl 2 A solution feed line and an NMP feed line.
Preferably, the number of the evaporators is two, namely a first evaporator and a second evaporator, and the static mixer, the extraction tower, the first evaporator, the second evaporator, the settling chamber, the mixed solvent preparation tank, the water removal tower and the composite solvent storage tank are sequentially connected; the outlet of the bottom of the first evaporator is connected with a first forced circulation pump, the outlet of the first forced circulation pump is divided into two branches, one branch is connected with the lower inlet of the first evaporator through a first heat exchanger, and the other branch is connected with the upper inlet of the second evaporator; the outlet of the bottom of the second evaporator is connected with a second forced circulation pump, the outlet of the second forced circulation pump is divided into two branches, one branch is connected with the inlet of the lower part of the second evaporator through a second heat exchanger, and the other branch is connected with a centrifugal machine; the lower outlet of the second evaporator is connected with the inlet of the sedimentation chamber through a pipeline. The first forced circulation pump and the second forced circulation pump can prevent NaCl crystals from blocking an output pipeline, and can circularly heat the NaCl crystals, so that the temperature in the first evaporator and the temperature in the second evaporator are constant.
Preferably, a preheater is arranged on the overflow path between the extraction tower and the evaporator; a pipeline between the centrifugal machine and the sedimentation chamber is provided with a third heat exchanger, and a pipeline connected with the lower outlet of the second evaporator is connected with the sedimentation chamber through the third heat exchanger; a fourth heat exchanger is arranged on a pipeline between the mixed solvent preparation tank and the water removal tower; the bottom outlet of the water removal tower is divided into two branches, wherein one branch is connected with the lower inlet of the water removal tower through a reboiler by a pipeline, and the other branch is connected with a composite solvent storage tank through a first condenser by a pipeline.
Preferably, the top parts of the first evaporator, the second evaporator and the water removal tower are connected with a vacuum pump through pipelines and the second condenser; the vacuum pump pumps out the gas phase at the upper parts of the first evaporator, the second evaporator and the water removal tower, and condenses and collects most of the organic wastewater, and a small part of the organic wastewater is subjected to A/O process treatment. The recovered upper gas phase can be condensed and then recycled as condensed water through vacuum treatment, and NMP is contained in the gas phase, so that the NMP can be prevented from being discharged to the atmosphere after condensation and collection, and the environment is polluted.
Further preferably, the outlet of the second condenser is connected with the inlet of the condensate storage tank through a pipeline, the outlet of the condensate storage tank is divided into three branches, namely a first condensate conveying pipeline, a condensate discharging pipeline and a second condensate conveying pipeline, the first condensate conveying pipeline is connected with the top inlet of the settling chamber, and the second condensate conveying pipeline is connected with the upper inlet of the water removal tower.
Preferably, the bottom outlet of the settling chamber is connected with the inlet of the centrifuge through a pipeline, and the lower outlet of the settling chamber is connected with the top inlet of the mixed solvent preparation tank through a pipeline. The crystals were further cooled in a settling chamber and the precipitated NaCl crystals were transferred to a centrifuge.
Preferably, the outlet of the centrifuge is connected to the settling chamber via a pipeline via a separation pump.
A recovery treatment process of salt-containing organic wastewater in the para-aramid production process comprises the following steps:
(1) Extraction: mother liquor and CHCl 3 Fully stirring in a static mixer to obtain a mixed solution, then feeding the mixed solution into an extraction tower, layering the mixed solution in the extraction tower, and then allowing an organic phase at the lower layer to communicate with CHCl 3 Discharging through a discharge pipeline, and overflowing the salt-containing organic wastewater at the upper layer of the extraction tower into an evaporator;
(2) Removing NaCl: concentrating the organic wastewater containing salt in an evaporator, separating out NaCl crystals at the bottom of the evaporator, separating the NaCl crystals from concentrated solution in the evaporator by a centrifugal machine, discharging NaCl solids through a NaCl discharge pipeline, and delivering the separated liquid into a settling chamber for further cooling and crystallization, and delivering the separated NaCl crystals to the centrifugal machine;
(3) Recycling: concentrate and condensate water of settling chamber, NMP and CaCl 2 Preparing the solution into a mixed solvent, wherein CaCl 2 、H 2 The mass ratio of O to NMP is (6-8): 20-25): 100, and then the mixed solvent enters a water removal tower for water removal, and enters a composite solvent storage tank for storage for standby.
Preferably, the method also comprises vacuum treatment, wherein the vapor phase at the upper part of the evaporator and the water removal tower is pumped out, condensed and collected for standby by a vacuum pump.
Preferably, the mother liquor of step (1) is combined with CHCl 3 The mass ratio of (2) is 1:4;
concentrating the organic wastewater containing salt in the step (2) sequentially by a first evaporator and a second evaporator, preheating the organic wastewater containing salt to 30-50 ℃ and then entering the first evaporator, wherein the vacuum degree in the first evaporator is-70 to-90 kpa, and the temperature is 65-75 ℃ (the concentration of salt after concentration is 6.84-8.63%); the vacuum degree in the second evaporator is-85 to-95 kpa, the temperature is 55 to 65 ℃ (after the second evaporator is used for concentration, caCl 2 The concentration is 40.72-41.65%, and the NaCl concentration in the salt-containing organic wastewater is 2.35-2.86%).
The liquid and the concentrated solution separated by the centrifuge in the step (2) are conveyed to a settling chamber after being cooled to 15-30 ℃, and the concentration of NaCl in the salt-containing organic wastewater is 1.93-2.21% after crystallization in the settling chamber.
In the step (3), the mixed solvent is heated to 100-115 ℃ and enters a water removal tower for water removal, the vacuum degree in the water removal tower is minus 85-minus 100kpa, the reflux temperature at the bottom of the water removal tower is 125-135 ℃, and the composite solvent after water removal is cooled to 10-80 ℃ and enters a composite solvent storage tank.
In the invention, the salt-containing organic wastewater is mother liquor, and the components in the mother liquor are CaCl 2 、NaCl、H 2 O, NMP the salt content is 3.5-5% (mass percent), caCl 2 The mass ratio of the NMP to NaCl is 4:1, and the NMP content is only 800-3000 PPM.
Compared with the prior art, the invention has the beneficial effects that:
1. the device and the process are suitable for continuously treating the salt-containing organic wastewater of the para-aramid solvent working section in an industrialized large scale (recycling the extracted inorganic phase), and fundamentally solve the problem that the salt-containing organic wastewater of the para-aramid solvent working section is difficult to treat;
2. the device and the process of the invention can remove NaCl in the organic wastewater containing salt, and the remained NMP and H 2 O、CaCl 2 The composite solvent is prepared by recycling and reusing and is used for a para-aramid polymerization working section, so that the cost of wastewater treatment is greatly reduced, useful components in the wastewater can be recycled, and the funds of outsourcing raw materials are reduced;
3. the bottoms of the first evaporator and the second evaporator are respectively provided with a forced circulation pump, so that NaCl crystals can be prevented from blocking an output pipeline, and circulating heating can be realized, and the constant temperature in the evaporators is ensured;
4. after the device and the process of the invention are used for treating the salt-containing organic wastewater, the removal rate of NaCl in the salt-containing organic wastewater reaches 86 percent, and CaCl in the mother liquor is simultaneously removed 2 NMP and H 2 And O is configured into a composite solvent for recycling.
Drawings
FIG. 1 is a schematic structural view of a device for recycling and treating organic wastewater containing salt in the para-aramid fiber production process;
in the figure: 1 is a mother liquor conveying pipeline and 2 is CHCl 3 The conveying pipeline 3 is a static mixer, 4 is a first conveying pump, 5 is an extraction tower, 6 is a second conveying pump, and 7 is CHCl 3 The discharge pipeline, 8 is a preheater, 9 is a first evaporator, 10 is a first forced circulation pump, 11 is a first heat exchanger, 12 is a third delivery pump, 13 is a second evaporator, 14 is a second forced circulation pump, 15 is a second heat exchanger, 16 is a fourth delivery pump, 17 is a centrifuge, 18 is a NaCl discharge pipeline, 19 is a separation pump, 20 is a fifth delivery pump, 21 is a third heat exchanger, 22 is a settling chamber, 23 is a sixth delivery pump, 24 is a seventh delivery pump, 25 is a mixed solvent preparation tank, 26 is a NMP feed pipeline, 27 is a CaCl feed pipeline 2 The solution feed line, 28 is eighth transfer pump, 29 is fourth heat exchanger, 30 is the water tower, 31 is ninth transfer pump, 32 is reboiler, 33 is first condenser, 34 is compound solvent storage tank, 35 is second condenser, 36 is vacuum pump, 37 is comdenstion water storage tank, 38 is tenth transfer pump, 39 is first comdenstion water transfer line, 40 is comdenstion water drain line, 41 is second comdenstion water transfer line.
Detailed Description
The invention is further illustrated, but not limited, by the following examples and figures.
It should be noted that the terms "first," "second," and the like in the description and in the claims of the present application are used for distinguishing between similar objects and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used may be interchanged where appropriate in order to describe the embodiments of the present application described herein.
Example 1
As shown in figure 1, the recovery treatment device of the organic wastewater containing salt in the para-aramid fiber production process comprises a static mixer 3, an extraction tower 5, a first evaporator 9, a second evaporator 13, a settling chamber 22, a mixed solvent preparation tank 25, a water removal tower 30 and a composite solvent storage tank 34 which are connected in sequence; the inlet of the static mixer 3 is respectively connected with a mother liquor conveying pipeline 1 and a mother liquor conveying pipelineCHCl 3 The lower outlet of the static mixer 3 is connected with the middle inlet of the extraction tower 5 through a first delivery pump 4 by a pipeline; the upper outlet of the extraction tower 5 is connected with a first evaporator 9 through an overflow pipeline, and the bottom outlet of the extraction tower 5 is connected with CHCl 3 Discharge line 7, CHCl 3 The discharge pipeline 7 is provided with a second delivery pump 6; the bottom outlet of the first evaporator 9 is connected with a first forced circulation pump 10, the outlet of the first forced circulation pump 10 is divided into two branches, one branch is connected with the lower inlet of the first evaporator 9 through a first heat exchanger 11, and the other branch is connected with the upper inlet of a second evaporator 13 through a third conveying pump 12; the outlet of the bottom of the second evaporator 13 is connected with a second forced circulation pump 14, the outlet of the second forced circulation pump 14 is divided into two branches, one branch is connected with the inlet of the lower part of the second evaporator 13 through a second heat exchanger 15, and the other branch is connected with a centrifugal machine 17 through a fourth conveying pump 16; the lower outlet of the second evaporator 13 is connected with the upper inlet of the sedimentation chamber 22 through a pipeline by a fifth delivery pump 20; the outlet of the centrifuge 17 is divided into two branches, one branch is connected with a NaCl discharge pipeline 18, and the other branch is connected with the upper inlet of a settling chamber 22 through a separation pump 19; the top inlet of the mixed solvent preparation tank 25 is connected with CaCl 2 A solution feed line 27 and an NMP feed line 26.
The first evaporator 9, the second evaporator 13 and the top outlet of the water removal column 30 are connected via a pipeline to a vacuum pump 36 via a second condenser 35. The outlet of the second condenser 35 is connected with the inlet of the condensate storage tank 37 through a pipeline, the outlet of the condensate storage tank 37 is connected with a condensate pipeline, the condensate pipeline is connected with a tenth delivery pump 38, the tail end of the condensate pipeline is divided into three branches, namely a first condensate delivery pipeline 39, a condensate external drainage pipeline 40 and a second condensate delivery pipeline 41, the first condensate delivery pipeline 39 is connected with the top inlet of the settling chamber 25, and the second condensate delivery pipeline 41 is connected with the upper inlet of the water removal tower 30.
A preheater 8 is arranged on the overflow pipe between the extraction tower 5 and the first evaporator 9; a third heat exchanger 21 is arranged on a pipeline between the centrifugal machine 17 and the sedimentation chamber 22, and a pipeline connected with the lower outlet of the second evaporator 13 is connected with the sedimentation chamber 22 through the third heat exchanger 21; an eighth transfer pump 28 and a fourth heat exchanger 29 are arranged on a pipeline between the mixed solvent preparation tank 25 and the water removal tower 30; the bottom outlet of the water removal tower 30 is divided into two branches, one branch is connected with the lower inlet of the water removal tower 30 through a pipeline via a ninth delivery pump 31 and a reboiler 32, and the other branch is connected with a compound solvent storage tank 34 through a pipeline via the ninth delivery pump 31 and a first condenser 33.
The bottom outlet of the settling chamber 22 is connected with the inlet of the centrifuge 17 through a sixth transfer pump 23 by a pipeline, and the lower outlet of the settling chamber 22 is connected with the top inlet of the mixed solvent preparation tank 25 through a seventh transfer pump 24 by a pipeline.
The recovery treatment process of the organic wastewater containing salt in the para-aramid fiber production process of the embodiment comprises the following steps:
(1) Extraction: mixing mother solution and CHCl in a mass ratio of 1:4 3 Via mother liquor conveying pipeline 1 and CHCl respectively 3 The conveying pipeline 2 is sent into a static mixer 3 to be fully stirred to obtain mixed liquor, then the mixed liquor is sent into an extraction tower 5, and after being layered by the extraction tower 5, the lower organic phase (extracted NMP and extractant CHCl) 3 ) By CHCl 3 The discharge pipeline 7 discharges the salt-containing organic wastewater (CaCl) at the upper layer of the extraction tower 2 、NaCl、H 2 O and a small amount of NMP, 3.5% salt, NMP content 1600 PPM) overflow through preheater 8 into first evaporator 9;
(2) Removing NaCl: the organic wastewater containing salt is concentrated in the first evaporator 9 and the second evaporator 13 in sequence. Firstly, preheating organic wastewater containing salt to 40 ℃ through a preheater 8, then entering a first evaporator 9, concentrating through the first evaporator 9, dividing the material into two parts through a first forced circulation pump 10 connected with the bottom of the first evaporator 9, wherein one part (reflux ratio is 1.6) flows back into the first evaporator 9 through a first heat exchanger 11, and the rest is pumped to a second evaporator 13 through a third delivery pump 12 for continuous concentration; after further concentration, the salt-containing wastewater in the second evaporator 13 is sequentially sent to a settling chamber 22 through a lower outlet of the second evaporator 13, a fifth conveying pump 20 and a third heat exchanger 21, naCl crystals are separated out from the bottom of the second evaporator 13, the NaCl crystals are divided into two parts through a second forced circulation pump 14 connected with the bottom, one part (with a reflux ratio of 1.7) flows back into the second evaporator 13 through a second heat exchanger 15, the rest is pumped to a centrifugal machine 17 (comprising NaCl crystals and concentrated solution in the second evaporator 13) through a fourth conveying pump 16 for separation, after separation, naCl solids are discharged through a NaCl discharge pipeline 18, the separated liquid is sequentially sent to the settling chamber 22 through a separation pump 19 and a third heat exchanger 21, the separated NaCl crystals are further cooled and crystallized in the settling chamber 22, and the separated NaCl crystals are conveyed to the centrifugal machine 17 again through a bottom outlet and a sixth conveying pump 23 for separation;
the vacuum degree in the first evaporator 9 is-80 kpa, the temperature is 70 ℃, and after the concentration of the first evaporator 9, the organic wastewater containing salt is concentrated to 7.43%; the vacuum degree in the second evaporator 13 is-88 kpa, the temperature is 60 ℃, and CaCl in the organic wastewater containing salt is further concentrated 2 The concentration of (2) and (3) NaCl is 40.93% and the concentration of NaCl is 2.44%, specifically, the mass ratio of calcium chloride, sodium chloride and water is about 3:0.19:4.127 after the concentration by the second evaporator 13;
(3) Recycling: the concentrated solution in the settling chamber 22 is sent to a mixed solvent preparation tank 25 through a lower outlet and a seventh delivery pump 24, and is respectively sent to a first condensed water delivery pipeline 39, an NMP feeding pipeline 26 and CaCl 2 The solution feed line 27 feeds condensed water, NMP and CaCl from the mixed solvent formulation tank 25 2 Preparing the solution into a mixed solvent, wherein CaCl 2 、H 2 The mass ratio of O to NMP is 7:20:100, then the mixed solvent is sent to a water removal tower 30 through an eighth conveying pump 28 and a fourth heat exchanger 29, the composite solvent after water removal is divided into two parts, one part (reflux ratio is 1.4) enters the water removal tower 30 for reflux through a bottom outlet of the water removal tower 30, a ninth conveying pump 31, a reboiler 32 and a lower inlet of the water removal tower 30, and the rest enters a composite solvent storage tank 34 for storage through the bottom outlet of the water removal tower 30, the ninth conveying pump 31 and a first condenser 33;
(4) Vacuum treatment: the gas phase of the first evaporator 9, the second evaporator 13 and the upper part of the water removal tower 30 is pumped out by a vacuum pump 36, condensed by a second condenser 35 and collected in a condensed water storage tank 37 for standby, part of condensed water collected in the condensed water storage tank 37 is sent to a mixed solvent preparation tank 25 by a first condensed water conveying pipeline 39, part of the condensed water is sent to the water removal tower 30 by a second condensed water conveying pipeline 41, and the rest of the condensed water is discharged by a condensed water discharging pipeline 40.
The liquid and the concentrated solution separated by the centrifuge 17 in the step (2) are conveyed to a settling chamber 22 after being cooled to 20 ℃ by a third heat exchanger 21, and after being crystallized by the settling chamber 22, the concentration of NaCl in the saline organic wastewater is 2.07 percent, and the mass ratio of calcium chloride, sodium chloride and water is about 3:0.14:4.127; in the step (3), the mixed solvent is heated to 110 ℃ by a fourth heat exchanger 29 and enters a water removal tower 30 for water removal, the vacuum degree in the water removal tower 30 is-92 kpa, the reflux temperature at the bottom of the water removal tower 30 is 130 ℃, and the composite solvent after water removal is cooled to 10-80 ℃ by a first condenser 33 and enters a composite solvent storage tank 34 for use in a polymerization working section of para-aramid fiber.
In the invention, the materials used for the first evaporator 9, the second evaporator 13, the pump, the pipeline, the centrifugal machine and other overflow parts are titanium steel alloy, titanium 2 or titanium 10.
Through the device and the process of the embodiment, the removal rate of NaCl in the salt-containing organic wastewater reaches 86 percent, and simultaneously CaCl in the mother liquor 2 NMP and H 2 And O is configured into a composite solvent for recycling.
It should be noted that: the polymerization of para-aramid is carried out by CaCl 2 NMP is used as a solvent, and HCl/NMP is generated at the same time of forming a polymer (poly (paraphenylene terephthalamide)), wherein HCl gas is dissolved in NMP liquid to form HCl/NMP solution, so that the HCl/NMP solution shows strong acidity and needs to be neutralized. The proposal uses NaOH to neutralize, and generates NaCl after neutralization, and CaCl is contained in the solvent 2 The salts in such a solution are NaCl and CaCl 2 Two kinds. Neutralization with NaOH is performed because its purity is easily very high.
Claims (10)
1. The recovery treatment device for the organic wastewater containing salt in the para-aramid fiber production process is characterized by comprising a static mixer, an extraction tower, an evaporator, a settling chamber, a mixed solvent preparation tank, a water removal tower and a composite solvent storage tank which are connected in sequence;
the inlets of the static mixers are respectively connected withIs connected with a mother liquor conveying pipeline and CHCl 3 A delivery line;
the upper outlet of the extraction tower is connected with the evaporator through an overflow pipeline, and the bottom outlet of the extraction tower is connected with CHCl 3 A discharge line;
the bottom outlet of the evaporator is connected with a centrifugal machine through a pipeline, the outlet of the centrifugal machine is divided into two branches, one branch is connected with a NaCl discharge pipeline, and the other branch is connected with the inlet of the settling chamber;
the top inlet of the mixed solvent preparation tank is respectively connected with a water conveying pipeline and CaCl 2 A solution feed line and an NMP feed line.
2. The recovery treatment device for organic wastewater containing salt in the para-aramid fiber production process according to claim 1, wherein the number of the evaporators is two, namely a first evaporator and a second evaporator, and the static mixer, the extraction tower, the first evaporator, the second evaporator, the settling chamber, the mixed solvent preparation tank, the water removal tower and the composite solvent storage tank are sequentially connected;
the outlet of the bottom of the first evaporator is connected with a first forced circulation pump, the outlet of the first forced circulation pump is divided into two branches, one branch is connected with the inlet of the lower part of the first evaporator through a first heat exchanger, and the other branch is connected with the inlet of the upper part of the second evaporator; the outlet of the bottom of the second evaporator is connected with a second forced circulation pump, the outlet of the second forced circulation pump is divided into two branches, one branch is connected with the inlet of the lower part of the second evaporator through a second heat exchanger, and the other branch is connected with a centrifugal machine;
the lower outlet of the second evaporator is connected with the inlet of the sedimentation chamber through a pipeline.
3. The recovery treatment device for organic wastewater containing salt in the para-aramid fiber production process according to claim 2, wherein a preheater is arranged on an overflow pipe between the extraction tower and the evaporator; a pipeline between the centrifugal machine and the sedimentation chamber is provided with a third heat exchanger, and a pipeline connected with the lower outlet of the second evaporator is connected with the sedimentation chamber through the third heat exchanger; a fourth heat exchanger is arranged on a pipeline between the mixed solvent preparation tank and the water removal tower; the bottom outlet of the water removal tower is divided into two branches, wherein one branch is connected with the lower inlet of the water removal tower through a reboiler by a pipeline, and the other branch is connected with a composite solvent storage tank through a first condenser by a pipeline.
4. The recovery treatment device for organic wastewater containing salt in the para-aramid fiber production process according to claim 2, wherein the tops of the first evaporator, the second evaporator and the water removal tower are connected with a vacuum pump through a pipeline and the second condenser.
5. The recovery treatment device for organic wastewater containing salt in the para-aramid fiber production process according to claim 4, wherein an outlet of the second condenser is connected with an inlet of the condensed water storage tank through a pipeline, the outlet of the condensed water storage tank is divided into three branches, namely a first condensed water conveying pipeline, a condensed water discharging pipeline and a second condensed water conveying pipeline, the first condensed water conveying pipeline is connected with a top inlet of the settling chamber, and the second condensed water conveying pipeline is connected with an upper inlet of the water removal tower.
6. The recovery treatment device for organic wastewater containing salt in the para-aramid fiber production process according to claim 1 or 2, wherein the bottom outlet of the settling chamber is connected with the inlet of the centrifuge through a pipeline, and the lower outlet of the settling chamber is connected with the top inlet of the mixed solvent preparation tank through a pipeline.
7. The recovery treatment device for organic wastewater containing salt in the para-aramid fiber production process according to claim 1 or 2, wherein the outlet of the centrifuge is connected with the settling chamber through a pipeline by a separation pump.
8. The recovery treatment process of the organic wastewater containing salt in the para-aramid fiber production process is characterized by comprising the following steps of:
(1) Extraction: mother liquor and CHCl 3 Fully stirring in a static mixerObtaining a mixed solution, then the mixed solution enters an extraction tower, and after layering by the extraction tower, the organic phase at the lower layer passes through CHCl 3 Discharging through a discharge pipeline, and overflowing the salt-containing organic wastewater at the upper layer of the extraction tower into an evaporator;
(2) Removing NaCl: concentrating the organic wastewater containing salt in an evaporator, separating out NaCl crystals at the bottom of the evaporator, separating the NaCl crystals from concentrated solution in the evaporator by a centrifugal machine, discharging NaCl solids through a NaCl discharge pipeline, allowing the separated liquid to enter a settling chamber, further cooling and crystallizing, and conveying the separated NaCl crystals to the centrifugal machine;
(3) Recycling: concentrate and condensate water of settling chamber, NMP and CaCl 2 Preparing the solution into a mixed solvent, wherein CaCl 2 、H 2 The mass ratio of O to NMP is (6-8): 20-25): 100, and then the mixed solvent enters a water removal tower for water removal, and enters a composite solvent storage tank for storage for standby.
9. The process for recycling organic wastewater containing salt in the para-aramid fiber production process according to claim 8, which is characterized by further comprising vacuum treatment, wherein the vapor phase at the upper parts of the evaporator and the water removal tower is pumped out, condensed and collected for standby by a vacuum pump.
10. The process for recycling organic wastewater containing salt in the para-aramid fiber production process according to claim 8, wherein the mother liquor and CHCl in the step (1) are 3 The mass ratio of (2) is 1:4;
concentrating the organic wastewater containing salt in the step (2) sequentially through a first evaporator and a second evaporator, preheating the organic wastewater containing salt to 30-50 ℃ and then entering the first evaporator, wherein the vacuum degree in the first evaporator is-70 to-90 kpa, and the temperature is 65-75 ℃; the vacuum degree in the second evaporator is-85 to-95 kpa, and the temperature is 55 to 65 ℃;
the liquid and the concentrated solution separated by the centrifuge in the step (2) are conveyed to a settling chamber after being cooled to 15-30 ℃;
in the step (3), the mixed solvent is heated to 105-115 ℃ and then enters a water removal tower for water removal, and the vacuum degree in the water removal tower is-85 DEG to the outside
100kpa, the reflux temperature of the bottom of the water removal tower is 125-135 ℃, and the composite solvent after water removal is cooled to 10-80 ℃ and then enters a composite solvent storage tank.
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