CN113735670A - Method for industrially producing sec-butyl lithium - Google Patents
Method for industrially producing sec-butyl lithium Download PDFInfo
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- CN113735670A CN113735670A CN202110998930.0A CN202110998930A CN113735670A CN 113735670 A CN113735670 A CN 113735670A CN 202110998930 A CN202110998930 A CN 202110998930A CN 113735670 A CN113735670 A CN 113735670A
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- WGOPGODQLGJZGL-UHFFFAOYSA-N lithium;butane Chemical compound [Li+].CC[CH-]C WGOPGODQLGJZGL-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 238000000034 method Methods 0.000 title claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 83
- 229910052744 lithium Inorganic materials 0.000 claims abstract description 81
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 72
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 229910052786 argon Inorganic materials 0.000 claims abstract description 36
- BSPCSKHALVHRSR-UHFFFAOYSA-N 2-chlorobutane Chemical compound CCC(C)Cl BSPCSKHALVHRSR-UHFFFAOYSA-N 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 32
- 229910052751 metal Inorganic materials 0.000 claims abstract description 30
- 239000002184 metal Substances 0.000 claims abstract description 30
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 26
- 239000012295 chemical reaction liquid Substances 0.000 claims abstract description 11
- 238000003825 pressing Methods 0.000 claims abstract description 11
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 239000007788 liquid Substances 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 18
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- RGSFGYAAUTVSQA-UHFFFAOYSA-N Cyclopentane Chemical compound C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 6
- 239000004215 Carbon black (E152) Substances 0.000 claims description 4
- 229930195733 hydrocarbon Natural products 0.000 claims description 4
- 150000002430 hydrocarbons Chemical group 0.000 claims description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims description 3
- 238000007086 side reaction Methods 0.000 abstract description 12
- 239000000047 product Substances 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- MZRVEZGGRBJDDB-UHFFFAOYSA-N N-Butyllithium Chemical compound [Li]CCCC MZRVEZGGRBJDDB-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 8
- 239000012300 argon atmosphere Substances 0.000 description 7
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000010992 reflux Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000004576 sand Substances 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000000460 chlorine Substances 0.000 description 5
- 229910052801 chlorine Inorganic materials 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000003999 initiator Substances 0.000 description 2
- 230000000977 initiatory effect Effects 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000002893 slag Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000003321 amplification Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000010960 commercial process Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- UBJFKNSINUCEAL-UHFFFAOYSA-N lithium;2-methylpropane Chemical compound [Li+].C[C-](C)C UBJFKNSINUCEAL-UHFFFAOYSA-N 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 150000002900 organolithium compounds Chemical class 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber Substances 0.000 description 1
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
- C07C1/26—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon starting from organic compounds containing only halogen atoms as hetero-atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
Abstract
The invention provides a method for industrially producing sec-butyl lithium. The method for industrially producing sec-butyl lithium comprises the following steps of (1) replacing air with argon in a reaction kettle, and adding a solvent; (2) putting the lithium particles into a feeder, replacing air with argon, and putting all the lithium particles into the reaction kettle; (3) starting stirring, dropwise adding 2-chlorobutane through a metering pump to react with lithium metal, and controlling the reaction temperature through a reaction kettle jacket and the feeding speed of the 2-chlorobutane; (4) keeping the temperature for 2-4 h, then using argon to press the reaction liquid into an intermediate tank, and keeping excessive lithium metal in the reaction kettle; (5) and (3) pressing the material liquid in the intermediate tank to a filter by using argon to remove lithium chloride solid, and obtaining colorless to light yellow transparent clear liquid, namely the sec-butyl lithium solution. The method adopts excessive metal lithium particles and 2-chlorobutane to react in a solvent at a certain temperature to produce sec-butyl lithium, thereby effectively avoiding side reaction and improving the yield.
Description
Technical Field
The invention relates to the technical field of chemical process and petrochemical industry, in particular to a method for industrially producing sec-butyl lithium.
Background
Butyl lithium is the most important organolithium compound, and n-butyl lithium, sec-butyl lithium and tert-butyl lithium are industrially produced. Butyl lithium has good reactivity, is mainly used in the polymer industry, and is an excellent initiator and catalyst for synthetic rubber. Butyl lithium is also widely used in organic synthesis, has the advantages of complete reaction, less by-products, easy separation of products and the like, and is used for preparing a plurality of valuable organic compounds and medicines.
The sec-butyl lithium is relatively active and has the fastest initiation speed to a polymerization monomer when being used as an initiator, so that when the sec-butyl lithium is used as the polymerization initiator, a polar solvent such as tetrahydrofuran is not required to be added into a polymerization system, and a solvent recovery system is simplified. The polymer produced using sec-butyllithium initiation has a narrow molecular weight distribution. The demand for sec-butyl lithium has increased year by year.
The common preparation method of the sec-butyl lithium is that the lithium metal reacts with the 2-chlorobutane in an inert hydrocarbon solvent, most of the lithium metal is prepared in a small scale in a laboratory at home and abroad at present, and some of the lithium metal are only prepared in a small scale at home and abroad, such as J Am. chem. Soc. 1941, 63, 9, 2479-containing 2482; J. am. chem. Soc. 1969, 91, 23, 6362-; european Journal of organic chemistry 2013, 24, 4136-4141, etc.
The literature for preparing sec-butyl lithium on a large scale is less, and metal lithium is firstly melted and stirred in white oil at 180-230 ℃, then is rapidly cooled to form lithium sand fine particles with phi of 40-250 mu m, and finally is filtered, washed by a solvent and put into a synthesis reaction kettle, such as the literature US 20070152354; raney filial, sec-butyl lithium synthesis [ J ], Lanhua technology, stage 03 of 1990.
The lithium sand preparation needs high temperature and rapid cooling, has high requirements on equipment and is complicated to operate; white oil is easy to remain in the product, and the product quality is affected. And the rapid temperature reduction in large-scale production is difficult to achieve, the metallic lithium is easy to agglomerate, and if the metallic lithium is cooled by cold water or frozen brine, the metallic lithium is inflammable and explosive when meeting water, so that great potential safety hazard exists. Meanwhile, the production of sec-butyl lithium is easy to generate a Woltz side reaction due to the reaction temperature and an amplification effect, so that the quality and the yield of the sec-butyl lithium are reduced.
Disclosure of Invention
Based on the technical problem, the invention aims to provide a novel method for industrially producing sec-butyl lithium more conveniently and efficiently. The method adopts the reaction of excessive metal lithium particles and 2-chlorobutane in a solvent at a certain temperature to produce sec-butyl lithium, thereby effectively avoiding side reaction and improving the yield.
The invention provides a method for industrially producing sec-butyl lithium. The method for industrially producing sec-butyl lithium comprises the following steps:
(1) replacing air with argon in the reaction kettle, and adding a solvent;
(2) putting the lithium particles into a feeder, replacing air with argon, and putting all the lithium particles into the reaction kettle;
(3) starting stirring, dropwise adding 2-chlorobutane through a metering pump to react with lithium metal, and controlling the reaction temperature through a reaction kettle jacket and the feeding speed of the 2-chlorobutane;
(4) keeping the temperature for 2-4 h, then using argon to press the reaction liquid into an intermediate tank, and keeping excessive lithium metal in the reaction kettle;
(5) the feed liquid in the intermediate tank was pressed against a filter with argon gas to remove the lithium chloride solid, and the obtained colorless to pale yellow transparent clear liquid, i.e., sec-butyl lithium solution was obtained.
Further, a lithium particle separation device is arranged in the reaction kettle.
Further, the solvent is a hydrocarbon solvent.
Further, the solvent is at least one of an n-pentane solvent, a cyclopentane solvent, an n-hexane solvent, a cyclohexane solvent, an n-heptane solvent and an octane solvent.
Furthermore, the diameter of the lithium particles is phi 2-15 mm, and the molar ratio of the metal lithium to the 2-chlorobutane is 2-4: 1.
Further, the reaction temperature of the metal lithium and the 2-chlorobutane is 30-40 ℃.
Further, the concentration of the sec-butyl lithium solution is 10-20%.
The method for industrially producing sec-butyl lithium adopts excessive metal lithium particles and 2-chlorobutane to react in a solvent at a certain temperature to produce sec-butyl lithium, effectively avoids side reaction and improves yield, and comprises the following specific steps: adding a solvent into a reaction kettle, adding lithium particles, starting stirring, dropwise adding 2-chlorobutane through a metering pump, and carrying out a micro-positive pressure reaction at 0-0.05 MPa in an argon atmosphere. After the reaction is finished, argon is used for pressing the reaction liquid into a middle tank, and unreacted excessive lithium metal is left in the reaction kettle through a special separation device and is directly used for the next batch of reaction. The feed liquid in the intermediate tank is pressed to a filter by argon gas to remove lithium chloride solid; the clear solution obtained was a solution of sec-butyllithium. The method of the invention directly uses commercial metal lithium particles without preparing lithium sand, and has simple and convenient operation; the large amount of excessive metal lithium (the excessive metal lithium is recycled), the side reaction is effectively inhibited, the quality of sec-butyl lithium is high, the requirements of industries such as petrifaction and pharmacy can be met, and the industrial production is realized.
The method for industrially producing sec-butyl lithium omits the processes of preparing lithium sand, such as high-temperature dispersion, rapid cooling, filtering and cleaning of metal lithium, and the like, simplifies the operation process, shortens the production period, improves the efficiency, saves energy, reduces consumption and reduces the production cost. The product has no white oil residue, and the quality is improved; in the whole process, the metal lithium, the sec-butyl lithium and the organic solvent are all in equipment such as a closed reaction kettle, a storage tank, a filter, a pipeline and the like, and meanwhile, the inert gas protects the equipment, so that the contact of the raw materials and products with sensitive substances such as air, water and the like is avoided, and the safety, reliability, stability and product quality of the production process are improved; the invention uses a special separation device to intercept unreacted metal lithium in the reaction kettle for recycling, increases the proportion of the metal lithium, can reduce the occurrence of side reactions such as Woltz and the like, improves the yield and the quality of products, reduces the loss of the metal lithium and is convenient for the treatment of lithium chloride slag.
Drawings
FIG. 1 is a reaction equation of metallic lithium and 2-chlorobutane in the commercial process for producing sec-butyllithium according to the present invention;
FIG. 2 is a process flow diagram of the method for industrially producing sec-butyl lithium of the present invention
Description of reference numerals:
1-feeder, 2-reaction kettle, 3-reflux condenser, 4-intermediate tank, 5-filter, 6-blending tank and 7-product storage tank.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Referring to fig. 1-2, the present invention provides a method for industrially producing sec-butyl lithium, comprising the following steps:
(1) replacing air with argon in the reaction kettle 2, and adding a solvent;
(2) putting the lithium particles into a feeder 1, replacing air with argon, and putting all the lithium particles into a reaction kettle;
(3) starting stirring, dropwise adding 2-chlorobutane through a metering pump to react with lithium metal, and controlling the reaction temperature through a reaction kettle jacket and the feeding speed of the 2-chlorobutane;
(4) keeping the temperature for 2-4 h, then pressing the reaction liquid into an intermediate tank 4 by using argon, and keeping excessive lithium metal in the reaction kettle;
(5) the feed liquid in the intermediate tank is pressed by argon gas to a filter 5 to remove lithium chloride solid, and the obtained colorless to light yellow transparent clear liquid, namely the solution of sec-butyl lithium, is sequentially conveyed to a preparation tank 6 and a product storage tank 7.
Further, a specially-made lithium particle separation device is arranged in the reaction kettle in the step (1).
The solvent in the step (1) is one or a mixed solvent of two or more of hydrocarbon solvents such as n-pentane, cyclopentane, n-hexane, cyclohexane, n-heptane, octane and the like.
Furthermore, the diameter of the lithium particles in the step (2) is phi 2-15 mm, and the theoretical molar ratio of the lithium metal to the 2-chlorobutane is 2-4: 1 according to the reaction equation of FIG. 1. The metal lithium can be excessive by 50-100% in the first feeding process, so that the 2-chlorobutane is added into the reaction kettle to react with the metal lithium in a short time, the generated sec-butyl lithium is effectively prevented from reacting with the 2-chlorobutane, and side reactions such as Woltz reaction and the like are inhibited. And excessive metal lithium is left in the reaction kettle, and the feeding amount of each batch of metal lithium later can achieve the same effect only by the theoretical weight.
Further, in the step (3), the reaction temperature of the metal lithium and the 2-chlorobutane is 30-40 ℃. Since the reaction of 2-chlorobutane and metallic lithium is an exothermic reaction, the temperature in the reaction vessel gradually rises with the continuous addition of 2-chlorobutane, and side reactions are easily caused. The temperature is reduced by introducing cooling oil into a reaction kettle jacket and a reflux condenser 3, and the temperature is controlled to be 30-40 ℃ by dropping the 2-chlorobutane, so that side reactions caused by temperature rise are avoided.
Further, the heat preservation time in the step (4) is 2-4 hours, and the temperature is 30-40 ℃.
Further, the concentration of the sec-butyl lithium obtained in the step (5) is 10-20%, and a corresponding solvent can be added to prepare the required concentration.
Example 1:
a dry, clean 2000L reactor was purged with argon for 3 times and 1000L cyclohexane solvent was added. 60kg of lithium particles are put into a feeder, argon is filled to replace air for 2 times, and then the lithium particles are put into a reaction kettle. Starting the reaction kettle for stirring, dropwise adding 225L of 2-chlorobutane through a metering pump, and reacting under the micro-positive pressure of 0-0.05 MPa in the argon atmosphere for about 2 hours. The reaction releases heat, when the temperature rises to 30 ℃, the jacket of the reaction kettle and the reflux condenser are cooled by introducing cold oil, and the temperature is controlled to be 30-40 ℃. And (4) after the dropwise addition is finished, keeping the temperature of 30-40 ℃ for reaction for 3 hours, and after the reaction is finished, pressing the reaction liquid into a tundish by using argon. The feed in the tundish was pressed against the filter with argon to remove the lithium chloride solids and the filter residue was washed with 100L of cyclohexane to give 1200L of a pale yellow clear cyclohexane solution of sec-butyllithium, concentration: 14.0%, activity: 98.5%, heterobase: 0.18%, covalent chlorine: 0.01 percent.
Example 2:
700L of cyclohexane solvent was added to a 2000L reactor. 32kg of lithium particles were put into a feeder, argon gas was introduced to replace air for 2 times, and then the lithium particles were put into a reaction vessel. Starting the reaction kettle for stirring, dropwise adding 225L of 2-chlorobutane through a metering pump, and reacting under the micro-positive pressure of 0-0.05 MPa in the argon atmosphere for about 3 hours. The reaction releases heat, when the temperature rises to 30 ℃, the jacket of the reaction kettle and the reflux condenser are cooled by introducing cold oil, and the temperature is controlled to be 30-40 ℃. And (4) after the dropwise addition is finished, keeping the temperature of 30-40 ℃ for reaction for 2 hours, and after the reaction is finished, pressing the reaction liquid into a tundish by using argon. The feed in the tundish was pressed against the filter with argon to remove the lithium chloride solids, and the filter residue was washed with 100L of cyclohexane to give 900L of a pale yellow clear cyclohexane solution of sec-butyllithium, concentration: 18.5%, activity: 98.7%, heterobase: 0.16%, covalent chlorine: 0.01 percent.
Example 3:
800L of n-hexane solvent was added to a 2000L reactor. 30kg of lithium particles are put into a feeder, argon is filled to replace air for 3 times, and then the lithium particles are put into a reaction kettle. Starting the reaction kettle for stirring, dropwise adding 225L of 2-chlorobutane through a metering pump, and reacting under the micro-positive pressure of 0-0.05 MPa in the argon atmosphere for about 2 hours. The reaction releases heat, when the temperature rises to 30 ℃, the jacket of the reaction kettle and the reflux condenser are cooled by introducing cold oil, and the temperature is controlled to be 30-40 ℃. And (4) after the dropwise addition is finished, keeping the temperature of 30-40 ℃ for reaction for 2 hours, and after the reaction is finished, pressing the reaction liquid into a tundish by using argon. And (3) pressing the material in the intermediate tank into a filter by using argon to remove lithium chloride solids, washing filter residues by using 100L of n-hexane to obtain 1000L of colorless transparent n-hexane solution of sec-butyl lithium, wherein the concentration is 18.6 percent, and the activity is as follows: 98.4%, heterobase: 0.20%, covalent chlorine: 0.02 percent.
Example 4:
900L of n-heptane solvent was added to a 2000L reactor. 33kg of lithium particles were put into a feeder, argon gas was introduced to replace air for 2 times, and the lithium particles were put into a reaction vessel. Starting the reaction kettle for stirring, dropwise adding 225L of 2-chlorobutane through a metering pump, and reacting under the micro-positive pressure of 0-0.05 MPa in the argon atmosphere for about 2 hours. The reaction releases heat, when the temperature rises to 30 ℃, the jacket of the reaction kettle is communicated with the reflux condenser to cool the oil, and the temperature is controlled to be 30-40 ℃. And (4) after the dropwise addition is finished, keeping the temperature of 30-40 ℃ for reaction for 2 hours, and after the reaction is finished, pressing the reaction liquid into a tundish by using argon. The feed in the tundish was pressed against the filter with argon to remove the lithium chloride solids and the filter residue was washed with 100L of n-heptane to give 1100L of a colorless transparent n-heptane solution of sec-butyl lithium, 16.8% concentration, activity: 98.6%, heterobase: 0.18%, covalent chlorine: 0.01 percent.
Example 5:
1000L of n-pentane solvent was added to a 2000L reactor. 28kg of lithium particles are put into a feeder, argon is filled to replace air for 3 times, and then the lithium particles are put into a reaction kettle. Starting the reaction kettle for stirring, dropwise adding 225L of 2-chlorobutane through a metering pump, and reacting under the micro-positive pressure of 0-0.05 MPa in the argon atmosphere for about 2 hours. The reaction releases heat, when the temperature rises to 30 ℃, the jacket of the reaction kettle and the reflux condenser are cooled by introducing cold oil, and the temperature is controlled to be 30-40 ℃. And (4) after the dropwise addition is finished, keeping the temperature of 30-40 ℃ for reaction for 4 hours, and after the reaction is finished, pressing the reaction liquid into a tundish by using argon. The feed in the tundish was pressed against the filter with argon to remove the lithium chloride solids, and the filter residue was washed with 100L of n-pentane to give 1200L of a colorless transparent n-pentane solution of sec-butyl lithium, 17.3% in concentration, active: 98.5%, heterobase: 0.17%, covalent chlorine: 0.02 percent.
The method for industrially producing sec-butyl lithium adopts excessive metal lithium particles and 2-chlorobutane to react in a solvent at a certain temperature to produce sec-butyl lithium, effectively avoids side reaction and improves yield, and comprises the following specific steps: adding a solvent into a reaction kettle, adding lithium particles, starting stirring, dropwise adding 2-chlorobutane through a metering pump, and carrying out a micro-positive pressure reaction at 0-0.05 MPa in an argon atmosphere. After the reaction is finished, argon is used for pressing the reaction liquid into a middle tank, and unreacted excessive lithium metal is left in the reaction kettle through a special separation device and is directly used for the next batch of reaction. The feed liquid in the intermediate tank is pressed to a filter by argon gas to remove lithium chloride solid; the clear solution obtained was a solution of sec-butyllithium. The method of the invention directly uses commercial metal lithium particles without preparing lithium sand, and has simple and convenient operation; the large amount of excessive metal lithium (the excessive metal lithium is recycled), the side reaction is effectively inhibited, the quality of sec-butyl lithium is high, the requirements of industries such as petrifaction and pharmacy can be met, and the industrial production is realized.
The method for industrially producing sec-butyl lithium omits the processes of preparing lithium sand, such as high-temperature dispersion, rapid cooling, filtering and cleaning of metal lithium, and the like, simplifies the operation process, shortens the production period, improves the efficiency, saves energy, reduces consumption and reduces the production cost. The product has no white oil residue, and the quality is improved; in the whole process, the metal lithium, the butyl lithium and the organic solvent are all in equipment such as a closed reaction kettle, a storage tank, a filter, a pipeline and the like, and the inert gas protects the equipment, so that the contact of the raw materials and the products with sensitive substances such as air, water and the like is avoided, and the safety, reliability, stability and product quality of the production process are improved; the invention uses a special separation device to intercept unreacted metal lithium in the reaction kettle for recycling, increases the proportion of the metal lithium, can reduce the occurrence of side reactions such as Woltz and the like, improves the yield and the quality of products, reduces the loss of the metal lithium and is convenient for the treatment of lithium chloride slag.
The above examples only express embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the present invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (7)
1. The method for industrially producing sec-butyl lithium is characterized by comprising the following steps of:
(1) replacing air with argon in the reaction kettle, and adding a solvent;
(2) putting the lithium particles into a feeder, replacing air with argon, and putting all the lithium particles into the reaction kettle;
(3) starting stirring, dropwise adding 2-chlorobutane through a metering pump to react with lithium metal, and controlling the reaction temperature through a reaction kettle jacket and the feeding speed of the 2-chlorobutane;
(4) keeping the temperature for 2-4 h, then using argon to press the reaction liquid into an intermediate tank, and keeping excessive lithium metal in the reaction kettle;
(5) and (3) pressing the material liquid in the intermediate tank to a filter by using argon to remove lithium chloride solid, and obtaining colorless to light yellow transparent clear liquid, namely the sec-butyl lithium solution.
2. The method of claim 1, wherein the method comprises: and a lithium particle separation device is arranged in the reaction kettle.
3. The method of claim 2, wherein the method comprises: the solvent is a hydrocarbon solvent.
4. The method of claim 3, wherein the method comprises: the solvent is at least one of an n-pentane solvent, a cyclopentane solvent, an n-hexane solvent, a cyclohexane solvent, an n-heptane solvent and an octane solvent.
5. The method of claim 4, wherein the method comprises: the diameter of the lithium particles is phi 2-15 mm, and the molar ratio of the metal lithium to the 2-chlorobutane is 2-4: 1.
6. The method of claim 5, wherein the method comprises: the reaction temperature of the metal lithium and the 2-chlorobutane is 30-40 ℃.
7. The method of claim 6, wherein the method comprises: the concentration of the sec-butyl lithium solution is 10-20%.
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| CN202110998930.0A CN113735670A (en) | 2021-08-28 | 2021-08-28 | Method for industrially producing sec-butyl lithium |
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| CN202110998930.0A CN113735670A (en) | 2021-08-28 | 2021-08-28 | Method for industrially producing sec-butyl lithium |
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| CN1443767A (en) * | 2003-03-21 | 2003-09-24 | 中国石化集团巴陵石油化工有限责任公司 | Method for producing alkyl lithium |
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| CN101805360A (en) * | 2010-05-06 | 2010-08-18 | 江西赣锋锂业股份有限公司 | Novel synthesis process of lithium alkyl |
| CN103381483A (en) * | 2012-05-03 | 2013-11-06 | 中国石油化工股份有限公司 | Dispersing and adjusting agent capable of adjusting adjusting lithium graininess and application of same |
| CN105669374A (en) * | 2016-01-15 | 2016-06-15 | 上虞华伦化工有限公司 | Synthetic method of lithium methoxide |
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| US5211887A (en) * | 1990-11-29 | 1993-05-18 | Fmc Corporation | High purity alkyllithium compounds and process of preparation |
| US5523447A (en) * | 1995-06-07 | 1996-06-04 | Fmc Corporation | Organolithium process |
| CN1443767A (en) * | 2003-03-21 | 2003-09-24 | 中国石化集团巴陵石油化工有限责任公司 | Method for producing alkyl lithium |
| CN1740126A (en) * | 2004-08-26 | 2006-03-01 | 大连绿源药业有限责任公司 | Prepn process of 2,3-halogeno toluene |
| CN101805360A (en) * | 2010-05-06 | 2010-08-18 | 江西赣锋锂业股份有限公司 | Novel synthesis process of lithium alkyl |
| CN103381483A (en) * | 2012-05-03 | 2013-11-06 | 中国石油化工股份有限公司 | Dispersing and adjusting agent capable of adjusting adjusting lithium graininess and application of same |
| CN105669374A (en) * | 2016-01-15 | 2016-06-15 | 上虞华伦化工有限公司 | Synthetic method of lithium methoxide |
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