CN107652314B - A kind of preparation method of boron chloride tertiary amine complex compound - Google Patents
A kind of preparation method of boron chloride tertiary amine complex compound Download PDFInfo
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- CN107652314B CN107652314B CN201710859918.5A CN201710859918A CN107652314B CN 107652314 B CN107652314 B CN 107652314B CN 201710859918 A CN201710859918 A CN 201710859918A CN 107652314 B CN107652314 B CN 107652314B
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- -1 boron chloride tertiary amine Chemical class 0.000 title claims abstract description 27
- 150000001875 compounds Chemical class 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims abstract description 174
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 64
- 238000002425 crystallisation Methods 0.000 claims abstract description 60
- 230000008025 crystallization Effects 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 50
- 239000000463 material Substances 0.000 claims abstract description 48
- 238000004821 distillation Methods 0.000 claims abstract description 42
- 238000001035 drying Methods 0.000 claims abstract description 36
- 150000001412 amines Chemical class 0.000 claims abstract description 33
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000007788 liquid Substances 0.000 claims abstract description 24
- 230000006837 decompression Effects 0.000 claims abstract description 20
- 238000000746 purification Methods 0.000 claims abstract description 19
- 239000010808 liquid waste Substances 0.000 claims abstract description 17
- 239000012535 impurity Substances 0.000 claims abstract description 16
- 238000005245 sintering Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 16
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002699 waste material Substances 0.000 claims abstract description 13
- 230000008569 process Effects 0.000 claims abstract description 6
- 238000009825 accumulation Methods 0.000 claims abstract description 4
- 239000000047 product Substances 0.000 claims description 55
- 239000002002 slurry Substances 0.000 claims description 16
- 238000007664 blowing Methods 0.000 claims description 11
- 238000000605 extraction Methods 0.000 claims description 8
- 239000002994 raw material Substances 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 5
- 239000004744 fabric Substances 0.000 claims description 5
- 238000002386 leaching Methods 0.000 claims description 5
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000008020 evaporation Effects 0.000 claims description 4
- 238000005292 vacuum distillation Methods 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- 238000013517 stratification Methods 0.000 claims description 3
- 238000010257 thawing Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000011344 liquid material Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- 238000006467 substitution reaction Methods 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims 1
- 238000009423 ventilation Methods 0.000 claims 1
- 230000005587 bubbling Effects 0.000 abstract description 6
- 238000001816 cooling Methods 0.000 abstract description 5
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract 1
- 239000012453 solvate Substances 0.000 abstract 1
- 150000003141 primary amines Chemical class 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 239000006228 supernatant Substances 0.000 description 4
- 150000003512 tertiary amines Chemical class 0.000 description 4
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 210000003298 dental enamel Anatomy 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 150000003335 secondary amines Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 description 1
- 238000010980 drying distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- UQKAOOAFEFCDGT-UHFFFAOYSA-N n,n-dimethyloctan-1-amine Chemical compound CCCCCCCCN(C)C UQKAOOAFEFCDGT-UHFFFAOYSA-N 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F5/00—Compounds containing elements of Groups 3 or 13 of the Periodic Table
- C07F5/02—Boron compounds
- C07F5/022—Boron compounds without C-boron linkages
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Removal Of Specific Substances (AREA)
Abstract
A kind of preparation method of boron chloride tertiary amine complex compound, dimethyl octylame is pumped into reaction kettle, excessive boron chloride is passed through by certain mol proportion under stirring is cooling to be reacted, impurity amine complex is decomposed in constant temperature stirring after synthesis, dissolve using methanol solvate again and crystallisation by cooling, centrifuge use " bubbling+decompression " distillation technique material drying to obtain primary crystallization purification finished product after drying material；Crystallisation by cooling, centrifuge drying, " bubbling+decompression " distill to obtain secondary crystallization purification finished product again after waste liquid progress distillation and concentration after centrifuge dripping；Remaining product uses water extracting process all to recycle again in last secondary liquid waste, and recovery article is equal to single sintering product, puts into reaction kettle again and is recycled, and final finished product rewinding rate of accumulating is up to 95% or more；For the finished product purity of preparation up to 99.5%, simple process is controllably high-efficient；Distillation simultaneously and methanol solution extracted are all recycled without discharge, and environment friendly and pollution-free, accumulation finished product yield is high.
Description
Technical field
The present invention relates to complex compound preparation technical field more particularly to a kind of preparation sides of boron chloride tertiary amine complex compound
Method.
Background technique
Due to the strong lewis acid characteristic of its electron deficient pair, the aminated compounds of Yi Yuyou lone electron pair formed boron chloride
Co-ordinate covalent bond, and then generate complex compound, wherein boron chloride dimethyl octylame (octyl dimethyl tertiary amine) complex compound is one
The important organic boron intermediate of kind, boron chloride dimethyl-octa amine complex are painted mainly for the preparation of advanced epoxy resin, are applied
The curing agent and promotor of material.The common synthesis technology of boron chloride dimethyl-octa amine complex are as follows: by dimethyl octylame
(C10H23N it) is pumped into reaction kettle, 1:1 is passed through boron chloride (BCl3) gas in molar ratio, and stirring, cooling are reacted, and reaction is eventually
Product is released after knot, though the synthesis of this technique is simple, product quality is poor, and the content of tertiary amine is in dimethyl octylame raw material
97%, remaining is the impurity amine such as primary amine, secondary amine, and the binding force of impurity amine and boron chloride is poor, is easy to decompose, to cause
Residual amine and chloride ion content are high, acid big in product, and moisture and fusing point index are also undesirable, black, influence product
The product index of effect, such single sintering is as follows:
| Residual amine | Moisture | PH | Fusing point | Chloride ion | Appearance | Product purity |
| 3% | 0.2% | 3-3.5 | 20℃ | 2% | Brownish black | < 97% |
Summary of the invention
Technical problem solved by the invention is to provide a kind of preparation method of boron chloride tertiary amine complex compound, to solve
Disadvantage in above-mentioned background technique.
Technical problem solved by the invention is realized using following technical scheme:
A kind of preparation method of boron chloride tertiary amine complex compound, the specific steps are as follows:
(1) dimethyl octylame raw material is pumped into reaction kettle first, is then stretched bottom tube for excessive trichlorine by certain mol proportion
Change boron gas to be passed through to dimethyl octylame liquid level, stirring is reacted to maintain reactor temperature, while pressed from both sides in reaction kettle
Set is passed through refrigerated circulating water and is cooled down, and reaction terminates to obtain single sintering product；
(2) it is passed through thermostatical circulating water to reaction kettle again, be sufficiently stirred to decompose impurity amine complex, while using water ring
Boron chloride that is remaining in reaction kettle and decomposing is pumped into the preposition sealing lye tank (vat) of vacuum pump and absorbed by vacuum pump；
(3) after the boron chloride in step (2) in reaction kettle exhausts, reaction kettle, stirring are pumped into using methanol as solvent
Dissolution is then being passed through refrigerated circulating water to reaction kettle, and stirring carries out crystallizing to obtain primary crystallization slurry；
(4) after reactor temperature is fallen in step (3), primary crystallization slurry is put into centrifuge drying, is obtained once
Dry material and a waste liquid；
(5) dry material obtained by step (4) is put into distillation still, and is passed through thermostatical circulating water and is melted, then adopted
Being bubbled with drying compressed air combines the mode of vacuum decompression to be distilled, and after methanol is evaporated, blowing obtains primary crystallization purification
Finished product, rewinding rate 65%；
(6) waste liquid that centrifuge in step (4) is thrown away is put into distillation still again, then uses drying compressed air
Bubbling combines the mode of vacuum decompression to distill and is concentrated, and is then passed through refrigerated circulating water to distillation still again and is recrystallized, it
Step (4)~step (5) is repeated afterwards, obtains secondary crystallization purification finished product and secondary liquid waste, and primary crystallization purifies finished product and secondary knot
The accumulation rewinding rate of crystalline substance purification finished product is 85%；
(7) gained secondary liquid waste in step (6) is put into extraction kettle, clear water is added, after mixing evenly stratification, lower layer
For material, upper layer is the methanol solution (impure amine) that water extracts, and is then passed through refrigerated circulating water to extraction kettle, is used for lower layer
Material crystallizes integral solid-state, while the mutual solution of the methanol-water on upper layer being pumped；
(8) thermostatical circulating water thawing is passed through in material extracted in step (7), then using drying compressed air drum
Bubble combines the mode of vacuum decompression to distill removal residual methanol and water, and reclaimed materials is obtained after being evaporated；
(9) reaction kettle and new single sintering are put into again using gained reclaimed materials in step (8) as single sintering product
Product repeats step (2)~step (8), and final finished rewinding rate is up to 95% or more.
In the present invention, in step (1), boron trichloride gas intake and the molar ratio of dimethyl octylame raw material are a little higher than
1:1, i.e. boron chloride are slightly excessive, and for guaranteeing all reactions completely of all dimethyl octylames, while it is logical to control boron chloride
Gas velocity rate is not more than 60kg/h, and to maintain reactor temperature to be no more than 42 DEG C, refrigerating cycle coolant-temperature gage is -10 DEG C；Dimethyl
Octylame is synthesized with boron chloride belongs to exothermic reaction, needs to be passed through refrigerated circulating water and cools down, and reactor temperature is more than 45
DEG C, then boron chloride dimethyl-octa amine complex product starts to decompose.
In the present invention, in step (2), 42 DEG C of thermostatical circulating water is passed through to reaction kettle, being sufficiently stirred the resolving time is
2h is then that the impurity such as primary amine, secondary amine amine complex is allowed sufficiently to decompose (impurity amine complex is stablized not as good as tertiary amine complex compound) in advance,
Product is preserved and entered during subsequent condensation-crystallization to avoid impurity amine complex, and impurity amine complex enters production
It is also easily decomposed after product, to cause the deterioration of product.
In the present invention, in step (3), the methanol and single sintering product quality ratio of addition are 6:10；It is logical to reaction kettle
Enter -10 DEG C of refrigerated circulating water stirring to be crystallized, starting crystallization temperature is 12 DEG C, and blowing temperature is 5 DEG C after completing crystallization, knot
Brilliant time 12h；The impurity amine such as boron chloride dimethyl-octa amine complex and primary amine, secondary amine is dissolvable in water methanol, due to pure three
Boron chloride dimethyl-octa amine complex fusing point is 25-28 DEG C, and the fusing point of the amines such as primary amine, secondary amine, tertiary amine is far below -10
DEG C, therefore under the conditions of refrigerating cycle coolant-temperature gage is -10 DEG C, boron chloride dimethyl-octa amine complex is easy to crystallization and is precipitated,
And the tertiary amine of the impurity such as primary amine, secondary amine amine and decomposed will not crystallize precipitation, to reach crystallization and purification purpose.
In the present invention, in step (4), centrifuge filtering cloth mesh number is 200 mesh, and a small amount of frost is used during drying
Methanol carries out pouring leaching cleaning.
In the present invention, in step (5), constant temperature circulating coolant-temperature gage is 42 DEG C, and blowing temperature is 40 DEG C in distillation still, is used
Drying compressed air, which is bubbled, combines the mode of vacuum decompression to distill specifically comprises the processes of: it is to reveal after drying that drying compressed air, which is bubbled,
Compressed air of the point less than -40 DEG C is passed through liquid material in kettle from distillation still bottom and is bubbled, to remove methanol " solution-air " two
Increase methanol " solution-air " two-phase contact area while the vapour pressure that balances each other, promotes methanol evaporation；Vacuum distillation is using vacuum
Methanol " solution-air " biphase-equilibrium vapour pressure is removed, methanol evaporation is promoted；The two can be used alone, and be used in combination more efficient；By
Start to decompose when boron chloride dimethyl-octa amine complex product is at 45 DEG C, therefore 42 DEG C of constant temperature of vapo(u)rizing temperature setting, and methanol
64.5 DEG C of boiling point, therefore, it to be evaporated methanol, it is general by the way of vacuum distillation, but vacuum pump pressure distillation is often met with very
Empty pump power, pipe diameter, system sealing be not tight and distills the puzzlement that later period equilibrium methanol vapour pressure spreads the problems such as slow, effect
Rate is not high；Therefore distillation technique and vacuum decompression will be bubbled distill and be combined, the distillation mode of this " pulling in front and others push behind ", can by a kettle at
The methanol distillation technique of product foreshortens within 5h, greatly improves distillation efficiency.
In the present invention, step (5), step (6), in step (8), drying compressed air can be used and be bubbled distillation or vacuum
Vacuum distillation substitution drying compressed air, which is bubbled, combines the vacuum decompression mode methanol condensed distilling, while distilling out to collecting kettle
It recycles.
In the present invention, in step (6), the quantity of methyl alcohol of concentration is that volume reduces 50%；The freezing being passed through to distillation still follows
Ring coolant-temperature gage is -10 DEG C, and recrystallization temperature is 12 DEG C after a waste liquid distillation and concentration, and blowing temperature is 5 DEG C after completing crystallization, then
Crystallization time 12h.
In the present invention, in step (7), the clear water volume ratio of secondary liquid waste and addition is 4:1；Time of repose is for 24 hours；Object
Temperature is 5 DEG C when material crystallizes blocking completion；Material in the methanol of secondary liquid waste containing nearly 15% can not crystallize rewinding, by
In water and methanol infinitely dissolve, and boron chloride dimethyl-octa amine product is insoluble with water, at the same the impurity such as primary amine, secondary amine amine also with
Water is insoluble, therefore the clear water that volume ratio is 20% is added in secondary liquid waste, and water can extract rapidly methanol, and by product rejecting in
Outside；Boron chloride dimethyl-octa amine product density 0.89g/cm3, methanol density 0.79g/cm3, methanol and water (content 20%)
Mutual solution density 0.83g/cm3, general amine density about 0.76g/cm3, therefore, after stratification, boron chloride dimethyl octylame
Product is sunken to bottom, and the mutual solution of methanol-water and impurity amine then float on top, when being passed through -10 DEG C of refrigerated circulating waters, due to tri-chlorination
25-28 DEG C of fusing point of boron dimethyl-octa amine product just crystallizes into monolith solid in lower layer quickly, and methanol and amine fusing point are remote low
In this temperature, it will not crystallize and keep liquid, after supernatant liquid suction is clean, it is remaining that remaining material melts distillation removal
Up to reclaimed materials after methanol and water, the mutual solution of the methanol-water of extraction is reused after dewatering process.
In the present invention, in step (8), constant temperature circulating coolant-temperature gage is 42 DEG C, and the evaporated temperature of reclaimed materials is 40 DEG C.
The utility model has the advantages that the present invention uses methanol as solvent, high-purity trichlorine is made by crystallisation by cooling, centrifuge dripping, distillation
Change boron tertiary amine complex product, process is simply controllable, high-efficient；Methanol solution is recycled without discharge, environmentally friendly nothing simultaneously
Pollution, the recycling of material almost all, accumulation finished product yield are high.
Specific embodiment
In order to be easy to understand the technical means, the creative features, the aims and the efficiencies achieved by the present invention, tie below
Embodiment is closed, the present invention is further explained.
Embodiment 1
A kind of preparation method of boron chloride tertiary amine complex compound, the specific steps are as follows:
465kg dimethyl octylame (octyl dimethyl tertiary amine) is pumped into the enamel reaction still of 2T, stirs and be passed through -10
DEG C refrigerated circulating water, by the boron chloride of 350kg by the speed of 55kg/h be passed through below reaction kettle liquid level carry out heat release it is anti-
It answers, to maintain reactor temperature to be no more than 42 DEG C, reaction terminates to obtain single sintering product, and 42 DEG C are then passed through in reaction kettle
Thermostatical circulating water, 2h is sufficiently stirred, to decompose impurity amine complex, while using water ring vacuum pump by remaining in reaction kettle and
The boron chloride of decomposition is pumped into the preposition sealing lye tank (vat) of vacuum pump and absorbs；Then the methanol of 480kg is pumped into reaction kettle, is stirred
Dissolution is mixed, then -10 DEG C of refrigerated circulating water is being passed through, is obtaining primary crystallization slurry within stirred crystallization 12 hours, to warm in reaction kettle
After degree is down to 5 DEG C (12 DEG C of crystallization start temperature), primary crystallization slurry is put (same to centrifuge (200 mesh of filter cloth mesh number) drying
When carry out pouring leaching cleaning with a small amount of frost methanol), obtain a dry material and a waste liquid；Later by a dry material after drying
Distillation still is put into, (methanol condensed distilled out is extremely in conjunction with being distilled by the way of vacuum decompression using drying compressed air bubbling
Kettle is collected to recycle), and the thermostatical circulating water for being passed through 42 DEG C is melted, vacuum pump vacuum degree -0.098MPa, sucking rate
280m3/ h, power 7.5KW, pipe diameter 100mm, -40 DEG C of compressed air dew point, distillation temperature in the kettle rises to after distillation 5 hours
40 DEG C (being considered as methanol to be evaporated), then blowing obtains primary crystallization purification finished product 530kg；In a waste liquid collection for throwing away centrifuge
In (general collection 2 batch liquid waste processings primary) put into again to distillation still, equally subtracted using drying compressed air bubbling in conjunction with vacuum
The mode of pressure distills and is concentrated for 16 hours that (quantity of methyl alcohol of concentration is that volume reduces 50%, and the methanol condensed distilled out is to collecting
Kettle recycles), it then passes to -10 DEG C of refrigerated circulating water and carries out recrystallizing to obtain secondary crystallization slurry, temperature in the kettle drop to be distilled
After to 5 DEG C (12 DEG C of crystallization start temperature), secondary crystallization slurry is put into centrifuge drying, obtains secondary liquid waste and secondary dry
Secondary dry material is equally distilled 5 hours in such a way that drying compressed air is bubbled and combines vacuum decompression, obtains secondary knot by material
Crystalline substance purification finished product 340kg, average every kettle rewinding 170kg；Secondary liquid waste is amounted into about 800L and puts into extraction kettle, clear water is added
200L is stirred evenly, and is stood 24 hours, is then passed to -10 DEG C of refrigerated circulating water, temperature in the kettle to be extracted is down to 5 DEG C, is pumped
Supernatant liquid, then it is passed through 42 DEG C of thermostatical circulating water thawing lower layer's material, lower layer's material investment distillation still is then used into drying
Compressed air, which is bubbled, combines the mode of vacuum decompression to distill 5 hours, and 40 DEG C of temperature in the kettle to be distilled whens discharge, and obtain reclaimed materials
200kg is used reclaimed materials to be put into reaction kettle again as single sintering product, obtained in primary crystallization be purified to
Product, the index of secondary crystallization purification finished product are as follows:
| Residual amine | Moisture | PH | Fusing point | Chloride ion | Appearance | Product purity |
| ≤ 0.5% | ≤ 0.1% | 4-4.5 | 25-28℃ | ≤ 0.1% | White | >=99.5% |
Embodiment 2
A kind of preparation method of boron chloride tertiary amine complex compound, the specific steps are as follows:
465kg dimethyl octylame (octyl dimethyl tertiary amine) is pumped into the enamel reaction still of 2T, stirs and be passed through -10
DEG C refrigerated circulating water, by the boron chloride of 350kg by the speed of 55kg/h be passed through below reaction kettle liquid level carry out heat release it is anti-
It answers, to maintain reactor temperature to be no more than 42 DEG C, reaction terminates to obtain single sintering product；42 DEG C are then passed through in reaction kettle
Thermostatical circulating water, 2h is sufficiently stirred, to decompose impurity amine complex, while using water ring vacuum pump by remaining in reaction kettle and
The boron chloride of decomposition is pumped into the preposition sealing lye tank (vat) of vacuum pump and absorbs；Then the methanol of 500kg is pumped into reaction kettle, is stirred
Dissolution is mixed, while being passed through -10 DEG C of refrigerated circulating water, primary crystallization slurry is obtained within stirred crystallization 12 hours, to reactor temperature
After being down to 5 DEG C (12 DEG C of crystallization start temperature), primary crystallization slurry is put to centrifuge (200 mesh of filter cloth mesh number) drying (simultaneously
Carry out pouring leaching cleaning with a small amount of frost methanol), obtain a dry material and a waste liquid；A dry material after drying is thrown later
Enter distillation still, (methanol condensed distilled out is recycled to kettle is collected) is distilled using vacuum decompression mode, and be passed through 42 DEG C
Thermostatical circulating water melted, vacuum pump vacuum degree -0.098MPa, sucking rate 280m3/ h, power 7.5KW, pipe diameter
100mm, distillation temperature in the kettle rises to 40 DEG C (being considered as methanol to be evaporated) after distillation 8 hours, and then blowing obtains primary crystallization and is purified to
Product 510kg；(2 batch liquid waste processings of general collection are primary) is concentrated to be put into again to distillation still in a waste liquid for throwing away centrifuge,
Equally use vacuum decompression mode distill and be concentrated for 24 hours (quantity of methyl alcohol of concentration for volume reduction 50%, the first distilled out
Alcohol is condensed to collection kettle and is recycled), it then passes to -10 DEG C of chilled water recirculated water and carries out recrystallizing to obtain secondary crystallization slurry, to
After distillation temperature in the kettle is down to 5 DEG C (12 DEG C of crystallization start temperature), secondary crystallization slurry is put into centrifuge drying, is obtained secondary useless
Secondary dry material is equally carried out vacuum decompression and distilled 8 hours by liquid and secondary dry material, obtains secondary crystallization purification finished product
360kg, average every kettle rewinding 180kg；Secondary liquid waste is amounted into about 850L and puts into extraction kettle, clear water 250L is added, stirs evenly,
24 hours are stood, then passes to -10 DEG C of refrigerated circulating water, temperature in the kettle to be extracted is down to 5 DEG C, pumps supernatant liquid, then lead to
Enter 42 DEG C of thermostatical circulating water and melt lower layer's material, lower layer's material investment distillation still is then subjected to vacuum decompression and is distilled 8 hours,
It discharges at 40 DEG C of temperature in the kettle to be distilled, obtains reclaimed materials 190kg, produced reclaimed materials to be put into reaction kettle again as single sintering
Product use, obtained in primary crystallization purification finished product, secondary crystallization purification finished product index it is as follows:
| Residual amine | Moisture | PH | Fusing point | Chloride ion | Appearance | Product purity |
| ≤ 0.5% | ≤ 0.1% | 4-4.5 | 25-28℃ | ≤ 0.1% | White | >=99.5% |
Embodiment 3
A kind of preparation method of boron chloride tertiary amine complex compound, the specific steps are as follows:
465kg dimethyl octylame (octyl dimethyl tertiary amine) is pumped into the enamel reaction still of 2T, stirs and be passed through -10
DEG C refrigerated circulating water, by the boron chloride of 350kg by the speed of 55kg/h be passed through below reaction kettle liquid level carry out heat release it is anti-
It answers, to maintain reactor temperature to be no more than 42 DEG C, reaction terminates to obtain single sintering product, and 42 DEG C are then passed through in reaction kettle
Thermostatical circulating water, 2h is sufficiently stirred, to decompose impurity amine complex, while using water ring vacuum pump by remaining in reaction kettle and
The boron chloride of decomposition is pumped into the preposition sealing lye tank (vat) of vacuum pump and absorbs；Then the methanol of 450kg is pumped into reaction kettle, is stirred
Dissolution is mixed, while being passed through -10 DEG C of refrigerated circulating water, primary crystallization slurry is obtained within stirred crystallization 12 hours, to reactor temperature
After being down to 9 DEG C (12 DEG C of crystallization start temperature), primary crystallization slurry is put to centrifuge (200 mesh of filter cloth mesh number) drying (simultaneously
Carry out pouring leaching cleaning with a small amount of frost methanol), obtain a dry material and a waste liquid；A dry material after drying is thrown later
Enter distillation still, mode is bubbled using drying compressed air and is distilled (methanol condensed distilled out is recycled to kettle is collected), and
It is passed through 42 DEG C of thermostatical circulating water to be melted, -40 DEG C of compressed air dew point, distillation temperature in the kettle rises to 40 after distillation 12 hours
DEG C (being considered as methanol to be evaporated), then blowing obtains primary crystallization purification finished product 490kg；It is concentrated in a waste liquid for throwing away centrifuge
(2 batch liquid waste processings of general collection are primary) is put into again to distillation still, and it is small equally to distill 30 using drying compressed air bubbling mode
Shi Jinhang concentration (quantity of methyl alcohol of concentration is that volume reduces 50%, and the methanol condensed distilled out is recycled to kettle is collected), then leads to
Enter -10 DEG C of refrigerated circulating water to carry out recrystallizing to obtain secondary crystallization slurry, (crystallization starts after temperature in the kettle to be distilled is down to 5 DEG C
12 DEG C of temperature), secondary crystallization slurry is put into centrifuge drying, secondary liquid waste and secondary dry material are obtained, equally by secondary dry
Material is dried compressed air and is bubbled distillation 12 hours, obtains secondary crystallization purification finished product 390kg, average every kettle rewinding 195kg；
Secondary liquid waste is amounted into about 750L and puts into extraction kettle, clear water 220L is added, stirs evenly, 24 hours is stood, then passes to -10 DEG C
Refrigerated circulating water, temperature in the kettle to be extracted is down to 5 DEG C, pumps supernatant liquid, then passes to 42 DEG C of thermostatical circulating water and melts
Lower layer's material investment distillation still is then dried compressed air and is bubbled distillation 12 hours, temperature in kettle to be distilled by lower layer's material
Discharging when spending 40 DEG C obtains reclaimed materials 210kg, uses reclaimed materials to be put into reaction kettle again as single sintering product, wherein
Resulting primary crystallization purification finished product, the index of secondary crystallization purification finished product are as follows:
| Residual amine | Moisture | PH | Fusing point | Chloride ion | Appearance | Product purity |
| ≤ 0.5% | ≤ 0.1% | 4-4.5 | 25-28℃ | ≤ 0.1% | White | >=99.5% |
。
Basic principles and main features and major advantage of the invention have been shown and described above.The technical staff of the industry
It should be appreciated that the present invention is not limited to the above embodiments, the above embodiments and description only describe the present invention
Principle, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these variation and
Improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention is by appended claims and its equivalent
Object defines.
Claims (10)
1. a kind of preparation method of boron chloride tertiary amine complex compound, which is characterized in that specific step is as follows:
(1) dimethyl octylame raw material is pumped into reaction kettle first, is then stretched bottom tube for excessive boron chloride by certain mol proportion
Gas is passed through to dimethyl octylame liquid level, and stirring is reacted to maintain reactor temperature, while logical in reacting kettle jacketing
Enter refrigerated circulating water to be cooled down, reaction terminates to obtain single sintering product；
(2) it is passed through thermostatical circulating water to reaction kettle again, be sufficiently stirred to decompose impurity amine complex, while using Water-ring vacuum
Boron chloride that is remaining in reaction kettle and decomposing is pumped into the preposition sealing lye tank (vat) of vacuum pump and absorbed by pump；
(3) after the boron chloride in step (2) in reaction kettle exhausts, using methanol as solvent be pumped into reaction kettle, stirring and dissolving,
It then is being passed through refrigerated circulating water to reaction kettle, stirring carries out crystallizing to obtain primary crystallization slurry；
(4) after reactor temperature is fallen in step (3), primary crystallization slurry is put into centrifuge drying, obtains a dry
Material and a waste liquid；
(5) dry material obtained by step (4) is put into distillation still, and is passed through thermostatical circulating water and is melted, then using dry
Dry compressed air, which is bubbled, combines the mode of vacuum decompression to be distilled, and after methanol is evaporated, blowing obtains primary crystallization purification finished product,
Rewinding rate 65%；
(6) waste liquid that centrifuge in step (4) is thrown away is put into distillation still again, is then bubbled using drying compressed air
It distills and is concentrated in conjunction with the mode of vacuum decompression, be then passed through refrigerated circulating water to distillation still again and recrystallized, Zhi Houchong
Multiple step (4)~step (5), obtains secondary crystallization purification finished product and secondary liquid waste, and primary crystallization purification finished product is mentioned with secondary crystallization
The accumulation rewinding rate of pure finished product is 85%；
(7) gained secondary liquid waste in step (6) is put into extraction kettle, clear water is added, stratification, lower layer are object after mixing evenly
Material, upper layer are the methanol solution that water extracts, then impure amine in methanol solution is passed through refrigerated circulating water to extraction kettle, and being used for will
Lower layer's material crystallizes integral solid-state, while the mutual solution of the methanol-water on upper layer being pumped；
(8) thermostatical circulating water thawing is passed through in material extracted in step (7), knot is then bubbled using drying compressed air
The mode for closing vacuum decompression distills removal residual methanol and water, and reclaimed materials is obtained after being evaporated；
(9) reaction kettle and new single sintering product are put into again using gained reclaimed materials in step (8) as single sintering product
It repeats step (2)~step (8), final finished rewinding rate is up to 95% or more.
2. a kind of preparation method of boron chloride tertiary amine complex compound according to claim 1, which is characterized in that step (1)
In, the molar ratio of boron trichloride gas intake and dimethyl octylame raw material is higher than 1:1, i.e. boron chloride is slightly excessive, for protecting
The all reactions completely of all dimethyl octylame raw materials are demonstrate,proved, while controlling boron chloride Ventilation Rate no more than 60kg/h, with dimension
Reactor temperature is held no more than 42 DEG C, refrigerating cycle coolant-temperature gage is -10 DEG C.
3. a kind of preparation method of boron chloride tertiary amine complex compound according to claim 1, which is characterized in that step (2)
In, 42 DEG C of thermostatical circulating water is passed through to reaction kettle, it is 2h that the resolving time, which is sufficiently stirred,.
4. a kind of preparation method of boron chloride tertiary amine complex compound according to claim 1, which is characterized in that step (3)
In, the methanol and single sintering product quality ratio of addition are 6:10；The refrigerated circulating water stirring for being passed through -10 DEG C to reaction kettle carries out
Crystallization, starting crystallization temperature is 12 DEG C, and blowing temperature is 5 DEG C after completing crystallization, crystallization time 12h.
5. a kind of preparation method of boron chloride tertiary amine complex compound according to claim 1, which is characterized in that step (4)
In, centrifuge filtering cloth mesh number is 200 mesh, and carries out pouring leaching cleaning using a small amount of frost methanol during drying.
6. a kind of preparation method of boron chloride tertiary amine complex compound according to claim 1, which is characterized in that step (5)
In, constant temperature circulating coolant-temperature gage is 42 DEG C, and blowing temperature is 40 DEG C in distillation still, is bubbled using drying compressed air and is subtracted in conjunction with vacuum
The mode of pressure is distilled specifically comprises the processes of: drying compressed air is bubbled the compressed air for dew point after drying less than -40 DEG C from steaming
It evaporates kettle bottom and is passed through liquid material in kettle and be bubbled, increase first while methanol " solution-air " biphase-equilibrium vapour pressure to remove
Alcohol " solution-air " two-phase contact area promotes methanol evaporation；Methanol " solution-air " biphase-equilibrium is removed in vacuo to use in vacuum distillation
Vapour pressure promotes methanol evaporation.
7. a kind of preparation method of boron chloride tertiary amine complex compound according to claim 1, which is characterized in that step (5),
In step (6), step (8), drying compressed air can be used and be bubbled distillation or vacuum decompression distillation substitution drying compressed air drum
The methanol condensed that bubble combines vacuum decompression mode to distill, while distilling out is recycled to kettle is collected.
8. a kind of preparation method of boron chloride tertiary amine complex compound according to claim 1, which is characterized in that step (6)
In, the quantity of methyl alcohol of concentration is that volume reduces 50%；The refrigerating cycle coolant-temperature gage being passed through to distillation still is -10 DEG C, and one time waste liquid steams
Recrystallization temperature is 12 DEG C after evaporating concentration, and blowing temperature is 5 DEG C after completing crystallization, recrystallizes time 12h.
9. a kind of preparation method of boron chloride tertiary amine complex compound according to claim 1, which is characterized in that step (7)
In, the clear water volume ratio of secondary liquid waste and addition is 4:1；Time of repose is for 24 hours.
10. a kind of preparation method of boron chloride tertiary amine complex compound according to claim 1, which is characterized in that step (8)
In, constant temperature circulating coolant-temperature gage is 42 DEG C, and the evaporated temperature of reclaimed materials is 40 DEG C.
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