The recovery processing method of lithium ion battery discharging waste gas N-Methyl pyrrolidone
Relate to the field
The present invention relates to lithium ion battery and make the recovery processing method of the relevant discharging waste gas N-Methyl pyrrolidone in field.
Background technology
The present invention is a kind of recovery processing method of lithium ion battery discharging waste gas N-Methyl pyrrolidone.The basic comprising of lithium ion battery has positive pole, negative pole, electrolytic solution and barrier film.In the manufacturing processed of lithium ion battery, to add tackiness agent to positive electrode material, negative material respectively and organic solvent carries out stirring to pulp, mix on the Copper Foil that is coated on as current collector, the aluminium foil, after the drying, make the positive and negative electrode of battery.N-Methyl pyrrolidone (1-Methyl-2-Pyrrolidone is hereinafter to be referred as NMP) has the flash-point height, and security is good, to advantage such as the dissolved dilution performance of tackiness agent PDVF is good and generally selected for use by the lithium ion battery manufacturing process.When oven dry, organic solvent NMP all becomes gas and with the air that heats, enters atmosphere through exhaust blower.
The physical data of NMP is as follows:
Molecular formula | Molecular weight | Boiling point/℃ | Density/(g/cm
3)
| Flash-point/℃ | Solvability |
C
5H
9NO
| ??99.13 | ????202 | ????1.0279 | ????95 | Miscible arbitrarily with water |
NMP is decided to be three class noxious chemicals in Germany, and allowing to enter atmospheric concentration is 100ppm.China is no standard still at present, but if directly discharging, its atmospheric level is higher than external required standard far away, is that a potential pollutes the source.NMP enters atmosphere, has also caused raw-material a large amount of waste simultaneously, lithium ion battery factory of family surplus in the of only Chinese domestic 60, and the present NMP that all use imports, about 2000 tons of year total consumption, value reaches 6,000 ten thousand yuan.Along with the increase of national lithium ion battery throughput, use the NMP annual consumption will reach 4800 tons, need about 1.44 hundred million yuan of consumption Renminbi.Therefore, reclaim NMP and be not only the Financial cost problem, and be the environmental protection problem, exploitation NMP reclaims novel process and relates to great economic benefit and environmental benefit.
At present, at the recovery data of organic solvent NMP seldom, the Chinese patent that we only find one piece of application number is 00123787.X, the treatment process that this patent adopts condensation to combine with absorption, adopt conventional condensation method that exhaust gas discharged in the lithium cell production is carried out degree of depth condensation earlier, condensing temperature is-10 ℃-0 ℃, gas after the uncooled that part of cooling passes through carbon fiber adsorption and catalytic combustion again, when absorption is saturated, carry out desorption with rare gas element and reclaim NMP, the purified gas attached through absorbing carbon fiber directly enters atmosphere.This method technical process is long, owing to adopt degree of depth condensation, energy consumption is higher.
Goal of the invention
The recovery technology novel method that the purpose of this invention is to provide a kind of lithium ion battery discharging waste gas N-Methyl pyrrolidone, this method adopts coagulates principle altogether, NMP is reclaimed in the agent of coagulating altogether that use can be dissolved each other with NMP and boiling point is lower, can realize under typical temperature, need not very low temperature.Therefore, flow process is simple, investment is little, less energy consumption, cost recovery are low, and can not produce the secondary pollution problem.
The invention scheme
The present invention is a kind of recovery processing method of lithium ion battery discharging waste gas N-Methyl pyrrolidone, it is characterized in that agent with fixed attention altogether by use can be dissolved each other with NMP and boiling point is lower, adopt " coagulating altogether " principle to reclaim N-Methyl pyrrolidone, technological process comprises that the hot industry waste gas that makes output in the lithium ion battery manufacturing passes through pretreatment unit under normal pressure, amount according to combustion gas temperature and the contained NMP of combustion gas is determined, so that NMP content is reached the ratio that 1.0-15 doubly measures, spray into the agent with fixed attention altogether of atomizing state, allow waste gas cool to 40-80 ℃, cool to 20-40 ℃ by condenser again, making NMP coagulate the agent condensation of together dissolving each other together gets off, reclaim liquid NMP concentration and reach the 20%-60% scope, the temperature of discharging gas is below 40 ℃, the NMP concentration of discharging gas is below the 100ppm, reclaim liquid and pass through rectification under vacuum purification column purification processes again, obtain the N-Methyl pyrrolidone finished product of purity 99.95% or more, and altogether with fixed attention agent can return and recycle.
The wherein agent with fixed attention altogether of the inventive method indication, it further is characterized as and can dissolves each other with N-Methyl pyrrolidone, and boiling point is than low 50 ℃-140 ℃ kind solvent of N-Methyl pyrrolidone and the mixture of solvent thereof, wherein can be the mixture of the different concns of two or more solvents arbitrarily in lower boiling single solvent such as water, ethanol, acetone, propyl alcohol or the above-mentioned all kinds of SOLVENTS.
The add-on of coagulating agent altogether of the inventive method indication is to determine according to the amount of combustion gas temperature and the contained NMP of combustion gas, as the preferred processing condition of the present invention, its further be characterized as altogether the add-on of coagulating agent be the amount of contained NMP in the waste gas 3-12 doubly;
Utilization is coagulated agent and NMP altogether and is had mutual solubility, and coagulate the principle that agent and NMP have different dividing potential drops altogether, when condensation, because NMP is more high than the boiling point that coagulates agent altogether, also be easy to condensation than coagulating agent altogether, therefore in the phlegma in the concentration ratio gas phase of NMP NMP concentration high, cause that to reclaim liquid concentration higher, reaching NMP is 20%-60%.This method is compared with common condensation method to be had at normal temperatures and can operate, and condensing temperature is lower than 40 ℃ and gets final product, and need not very low temperature etc. advantage.
Wherein the NMP concentration of the condensate recovery liquid that obtains through retrieving arrangement far can not satisfy the needs of reuse to the lithium ion battery manufacturing processed, make advanced treatment and must pass through purification column.Because the boiling point under the NMP normal pressure is very high, so be designed to the operating method of rectification under vacuum, with energy efficient and reduction running cost, the purity of process purification column NMP can reach more than 99.95% when reclaiming the liquid purification processes.
Why the present invention selects different agent and the melting concns thereof of coagulating altogether, and key will consider to coagulate altogether self cost impact of agent; And the mixture concentration difference causes altogether the difference that partial pressure difference does not cause the NMP concentration of common lime set to be produced when coagulating, and spraying dosage is for the influence of costs such as condensation cooling and follow-up rectification under vacuum purifying; That also have to select coagulates the secondary pollution etc. that agent can not cause removal process altogether.
Therefore, as one of preferred processing condition of the present invention, its agent of coagulating altogether that is further characterized in that employing is a deionized water, and so that NMP content is reached the ratio that 3-5 doubly measures, preferably the ratio of 4.5 times of amounts is sprayed and coagulated recycling altogether.
In addition, as preferred another processing condition of the present invention, its agent of coagulating altogether that is further characterized in that employing is deionized water and alcoholic acid mixture, preferably the aqueous ethanolic solution of 5% concentration is as coagulating agent altogether, and so that NMP content is reached the ratio that 8-12 doubly measures, preferably the ratio of 10 times of amounts is sprayed and is coagulated recycling altogether.
Specific embodiment
Embodiment 1:
100 ℃ organic exhaust gas during the lithium cell industrial gaseous waste is handled, the concentration of the contained NMP of waste gas is 1140ppm, under normal pressure, sprays into deionized water as coagulating agent altogether through atomization system, the add-on of deionized water is 4.5 times of contained NMP.Spent air temperture drops to 70 ℃, cools to 20 ℃ through condenser, obtains containing the solution of NMP, the concentration of this solution is 50.8%, and the concentration of emission gases is 80ppm, and nmp solution is through after the rectification under vacuum, obtain purity and be 99.97% NMP finished product, water content is 60ppm, the rate of recovery: 93%.
Embodiment 2:
The concentration of 120 ℃ of contained NMP of organic exhaust gas is 957ppm, under normal pressure, sprays into deionized water as coagulating agent altogether through atomization system, and the add-on of deionized water is 10 times of contained NMP.Spent air temperture drops to 62 ℃, cools to 30 ℃ through condenser, obtains containing the solution of NMP, the concentration of this solution is 33.6%, and the concentration of emission gases is 80ppm, and nmp solution is through after the rectification under vacuum, obtain purity and be 99.96% NMP finished product, water content is 85ppm, the rate of recovery: 91.7%.
Embodiment 3:
The concentration of 120 ℃ of contained NMP of organic exhaust gas is 1140ppm, under normal pressure, sprays into deionized water as coagulating agent altogether through atomization system, and the add-on of deionized water is 11.3 times of contained NMP.Spent air temperture drops to 53 ℃, cools to 35 ℃ through condenser, obtains containing the solution of NMP, the concentration of this solution is 26%, and the concentration of emission gases is 80ppm, and nmp solution is through after the rectification under vacuum, obtain purity and be 99.95% NMP finished product, water content is 98ppm.The rate of recovery: 93%.
Embodiment 4:
120 ℃ organic exhaust gas, the concentration of the contained NMP of waste gas are 957ppm, under normal pressure, the aqueous ethanolic solution that sprays into 5% concentration through atomization system is as coagulating agent altogether, add-on is 10 times of contained NMP, and spent air temperture drops to 64 ℃, cools to 30 ℃ through condenser, obtain containing the solution of NMP, the concentration of this solution is 36%, and the concentration of emission gases is 78ppm, and nmp solution is through after the rectification under vacuum, obtain purity and be 99.96% NMP finished product, water content is 80ppm.The rate of recovery: 92%.With embodiment 2 contrasts, after as seen the agent choosing had added ethanol with fixed attention altogether, the concentration of NMP had brought up to 36% by 33.6% in the lime set altogether, has obviously reduced the cost of follow-up rectification under vacuum.