CN108863821A - A kind of preparation method of polyhydric alcohol amine - Google Patents
A kind of preparation method of polyhydric alcohol amine Download PDFInfo
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- CN108863821A CN108863821A CN201810889199.6A CN201810889199A CN108863821A CN 108863821 A CN108863821 A CN 108863821A CN 201810889199 A CN201810889199 A CN 201810889199A CN 108863821 A CN108863821 A CN 108863821A
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/08—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups
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Abstract
The present invention relates to a kind of preparation methods of polyhydric alcohol amine, belong to field of chemical technology, include the following steps：In design equipment, the dichloropropane continuously flowed is reacted on solid catalyst with the hydramine that substep is added, and synthesizes polyhydric alcohol amine.The present invention provides a kind of dichloropropane deep working method, solve the problems, such as that dichloropropane other application approach pollutes environment, used catalyst can be regenerated and be reused, and belong to green chemical industry technique；The present invention provides a kind of polyhydric alcohol amine preparation method, and mild condition, operating cost is low, high production efficiency, polyhydric alcohol amine degree of functionality flexible adjustment, is suitble to industrialized production.
Description
Technical field
The present invention relates to a kind of preparation methods of polyhydric alcohol amine, belong to field of chemical technology.
Background technique
Chlorohydrination produces a large amount of dichloropropanes of epoxychloropropane byproduct in process.Dichloropropane carries out aminating reaction, passes through
The processes such as neutralization, concentration, desalination, rectifying obtain product propane diamine；Aminating reaction pressure is high, and risk is big, and last handling process produces
Raw a large amount of contaminated wastewater environment.Under the action of catalyst, dichloropropane carries out chlorination reaction in 490 DEG C of air streams and generates tetrachloro
Change carbon and tetrachloro-ethylene；Dichloropropane can produce chlorallylene and 1- chloropropene with pyrolytic；The chlorination and decomposition reaction
Condition is harsh, and equipment requirement is high.Propylene glycol is produced in dichloropropane hydrolysis, and the process product yield is low, a large amount of Nacls of by-product, together
When generate a large amount of industrial wastewaters.Currently, all there are no find this by-product of dichloropropane for domestic each production of propylene oxide producer
Effective utilization ways reduce propylene oxide and produce to further improve the comprehensive benefit of chlorohydrination production propylene oxide
The consumption of raw materials of product, it is urgency technical research project leaved for development that rationally processing, which utilizes by-product dichloropropane,.
Summary of the invention
To solve the above-mentioned problems, continuous using dichloropropane the present invention provides a kind of preparation method of polyhydric alcohol amine
Charging, hydramine substep are added operation and obtain pure product after vacuum extraction low boiling component after three sections of catalytic action.
The present invention is using dichloropropane and hydramine as raw material, under catalytic action, carries out substitution reaction.Reaction equation is as follows：
R1 in formula, R2 CH3, CH3CH2, CH3CH2CH2,CH3CH2CH2CH2,In one
Kind is several；R1 is identical or different with R2.The hydroxyl quantity of product is adjustable.
Polyhydric alcohol amine synthesising method reacting condition provided by the invention is mild, and operating cost is low, and product yield is high, for synthesis
It opened up a new way using dichloropropane, present invention process environmental protection, catalyst can be used with regeneration cycle, be suitble to industry metaplasia
It produces.
To achieve the goals above, the technical solution adopted by the present invention is：A kind of preparation method of polyhydric alcohol amine, including such as
Lower step：
Step 1：Catalyst preparation
It by the roasting of particle cocoanut active charcoal, alkali cleaning, pickling, then dries, later by particle cocoanut active charcoal, alkali or alkalinity
Oxide and rare earth element, which are uniformly mixed, to be placed in crucible, is placed in nitrogen atmosphere muffle furnace, so that alkali, rare earth element are molten
Melt and penetrate between active carbon duct and carbon-coating, interacts with particle cocoanut active charcoal surface group, form uniform solid phase, mistake
Column packed with catalyst is packed into after sieve, it is spare；
Step 2：Processing route
1 is added after dichloropropane and hydramine metering#Head tank, the uniform solution that dichloropropane and hydramine are formed is from 1#Catalysis
Column bottom enters 1#It is catalyzed column, after being reacted under the action of catalyst, from 1#Leave 1 in catalysis column top#It is catalyzed column and enters 2#It is high
Position slot, 2#It is sufficiently mixed in head tank with metered hydramine；Again from 2#It is catalyzed column bottom and enters 2#It is catalyzed column, is being catalyzed
After agent catalytic action, from 2#Leave 2 in catalysis column top#It is catalyzed column and enters 3#Head tank, 3#In head tank again with the hydramine of addition
Mixing；Again from 3#It is catalyzed column bottom and enters 3#It is catalyzed column, after carrying out catalysis reaction under the action of catalyst, from 3#It is catalyzed column top
Leave 3#Catalysis column enters product slot；Product slot obtains final product after deviating from low boiling component under vacuum system drive.
In step 1, cocoanut active charcoal roasts 3~6h in 250~350 DEG C of nitrogen atmosphere, it is cooling after with 1~
The sodium hydroxide or potassium hydroxide aqueous solution of 10mol/L impregnates 1~10h, distills water washing 2~6 times, 110~150 DEG C after filtering
After dry 3~12h, then with aqueous solution of nitric acid 1~12h of dipping of 1~10mol/L, then filtered cocoanut active charcoal is used
Distillation water washing 2~6 times, 110~150 DEG C of dry 3~12h.
In step 1, by cocoanut active charcoal, sodium hydroxide or hydroxide after roasting, alkali cleaning, pickling, drying process
Potassium and lanthanum nitrate or cesium nitrate, are placed in muffle furnace, 250~550 DEG C of roastings in nitrogen atmosphere, so that alkali, rare earth element
Group with coconut activated carbon surface obtains solid base catalyst by chemical bonds, is fitted into catalysis column, spare.
In step 2, it is additionally provided with following steps：Hydramine and dichloropropane are according to molar ratio 1:1 is added after 1~10 metering#
Head tank, 1#After being mixed to form uniform solution in head tank, from 1#A or 1#B is catalyzed column bottom and enters 1#A or 1#B is catalyzed column, or
Person enters 1 simultaneously#A and 1#B is catalyzed column, after carrying out catalysis reaction under the action of catalyst, from 1#Catalysis column top exits into 2#
Head tank, 2#From 1 in head tank#The material that catalysis column top is left is sufficiently mixed with metered hydramine, hydramine and 1#It is high
The dichloropropane molar ratio of the position original addition of slot is 1:1~10；Under the effect of gravity, 2#In head tank be uniformly mixed solution from
2#It is catalyzed column bottom and enters 2#A or 2#B is catalyzed column or 2#A and 2#B is catalyzed column, after catalyst effect, from 2#It is catalyzed column
Top exits into 3#Head tank；3#From 2 in head tank#The material and metered hydramine that catalysis column top is left are abundant
Mixing, hydramine and 1#The dichloropropane molar ratio that head tank is initially added is 1:1~10；Under the effect of gravity, 3#It is mixed in head tank
Uniform solution is closed from 3#It is catalyzed column bottom and enters 3#A or 3#B is catalyzed column or 3#A and 3#B is catalyzed column, anti-in catalyst
Ying Hou, from 3#Leave 3 in catalysis column top#Catalysis column enters product slot；Product tank liquor position is at 3/2nds to four/3rds, liquid
Position triggering starting vacuum system, obtains product after deviating from low boiling component；Wherein, 1#Being catalyzed column includes 1 be arranged in parallel#a、1#b
It is catalyzed column；2#Being catalyzed column includes 2 be arranged in parallel#a、2#B is catalyzed column；3#Being catalyzed column includes 3 be arranged in parallel#a、3#B is catalyzed column.
The dichloropropane is 1,2- dichloropropane or 1,3- dichloropropane or 1,2- dichloropropane and 1,3- bis-
Chloropropane mixed solution.
The hydramine isOrWherein R1, R2 CH3, CH3CH2,
CH3CH2CH2,CH3CH2CH2CH2,R1 is identical or different with R2.
Prepared catalyst is renewable after use, is recycled after regeneration.
In step 2,1#Head tank, hydramine and dichloropropane are according to molar ratio 1:It is added after 1~10 metering, preferably rubs
That ratio 1:2~6, after being mixed to form uniform solution, according to flow 500~1500mL/min flow velocity, under the effect of gravity from catalysis
Column bottom enters 1#A or 1#B is catalyzed column or 1#A and 1#B is catalyzed column, preferably enters 1#A or 1#B is catalyzed column, urges at 45~80 DEG C
Change in column and carries out catalysis reaction；Reaction system leaves reaction column into 2 from catalysis column top#Head tank, with metered alcohol
Amine is sufficiently mixed, hydramine and 1#It is 1 that dichloropropane molar ratio, which is added, in head tank:1~10, preferred molar ratio 1:2~6；In gravity
Under effect, uniformly mixed solution is from 2#It is catalyzed column bottom and enters 2#A or 2#B is catalyzed column or 2#A and 2#B be catalyzed column, preferably into
Enter 1#A or 1#B is catalyzed column, 2#It is catalyzed in column after 55~90 DEG C of completion catalytic action, reaction system is left instead from catalysis column top
Ying Zhu enters 3#Head tank.3#The metered hydramine of head tank is sufficiently mixed, hydramine and 1#Head tank is added dichloropropane and rubs
You are than being 1:1~10, preferred molar ratio 1:2~6,；Uniformly mixed solution under the effect of gravity, from 3#Column bottom is catalyzed to enter
3#A or 3#B is catalyzed column or 3#A and 3#B is catalyzed column, preferably enters 3#A or 3#B is catalyzed column, 3#65~100 DEG C are catalyzed in column
Catalysis reaction, reaction system leave reaction column from catalysis column top and enter product slot；When product tank liquor position reaches 3/4ths, liquid
Position triggering starting vacuum system, is automatically closed product slot inlet valve and products export valve, after deviating from low boiling component, closes vacuum
System opens outlet valve and obtains product.
In step 2, catalyst a column is in parallel with b column, can arbitrarily switch；When a column catalyst regeneration, open
After the valve of b column connecting pipe road, a column connecting pipe road valve is closed, it is living to restore catalyst to carry out regeneration treatment to a column catalyst
Property；Continuous production may be implemented in whole system；Conversely,.
Compared with prior art, the invention has the advantages that：It is successfully prepared consolidating with low-temperature catalyzed function
Body super base, catalyst have both bronsted alkali and Lewis base centers, by the adjusting of micro-moisture, realize catalyst surface
The conversion of bronsted alkali and lewis base, under different alkali centers act synergistically, so that catalyst has low temperature high activity.Dichloro
Propane mildly carries out reacting preparing polyhydric alcohol amine with hydramine at catalyst alkali center, and product yield is high；Catalyst can regenerate with
And be recycled, there are no pollution to the environment for reaction system, and reaction process is environmentally protective.
Detailed description of the invention
Fig. 1 is that polyhydric alcohol amine of the invention prepares path schematic diagram；
Fig. 2 is polyhydric alcohol amine preparation facilities figure；
Fig. 3 is polyhydric alcohol amine foam performance schematic diagram.
Specific embodiment
The present invention will be further described with reference to the accompanying drawings and examples.
According to fig. 2, hydramine and dichloropropane are added 1 after proportionally measuring#Head tank, after being mixed to form uniform solution,
Under the gravity of liquid, from 1#It is catalyzed column bottom and enters 1#It is catalyzed column, after carrying out catalysis reaction under the action of catalyst, instead
Answer system from 1#Reaction column is left into 2 in catalysis column top#Head tank, 2#From 1 in head tank#Leave anti-in catalysis column top
After answering system and metered hydramine to be sufficiently mixed, from 2#It is catalyzed column bottom and enters 2#It is catalyzed column, completes to react in set temperature
Afterwards, from 2#Reaction column is left into 3 in catalysis column top#Head tank, 3#From 2 in head tank#The reactant that catalysis column top is left
System is sufficiently mixed with metered hydramine, from 3#It is catalyzed column bottom and enters 3#It is catalyzed column, after completing setting reaction, material system
From 3#It leaves reaction column and enters product slot in catalysis column top；Product slot level set liquid level triggering starting vacuum system, i.e. product
When tank liquor position reach a certain height, vacuum system starts and obtains product, inspection after passing through vacuum distillation abjection low boiling component
It is tested for the property.
A kind of preparation method of polyhydric alcohol amine, includes the following steps：
Step 1：Catalyst preparation
Coconut husk charcoal is roasted into 3~6h in 250~350 DEG C of nitrogen atmosphere, with the sodium hydroxide of 1~10mol/L after cooling
Or potassium hydroxide aqueous solution impregnates 1~10h, distills after filtering water washing 2~6 times, after 110~150 DEG C of dry 3~12h, then uses
The aqueous solution of nitric acid of 1~10mol/L impregnates 1~12h, and filtered coconut husk charcoal is then distilled water washing 2~6 times, 110~
150 DEG C of dry 3~12h are spare.
The particle coconut husk charcoal that pretreatment is completed is mixed with sodium hydroxide or potassium hydroxide and lanthanum nitrate or cesium nitrate
Close uniformly, be placed in muffle furnace, 250~550 DEG C of 6~12h of roasting in nitrogen atmosphere so that sodium hydroxide, potassium hydroxide and
Lanthanum nitrate, cesium nitrate melting penetrate into active carbon duct and graphite layers, with particle coconut carbon surface carbon or group chemical
Bonding, obtains solid super basic catalyst, and filling is packed into catalysis column after screening.
Step 2：Processing route
Hydramine and dichloropropane in molar ratio 1:After 1~10 metering is mixed to form uniform solution, adjusting solution flow velocity is 500
~1500mL/min, under the effect of gravity, from 1#Head tank 1#Into 1#It is catalyzed column bottom, then from 1#It is catalyzed column bottom and enters 1#It urges
Change column, control 1#45~80 DEG C of column temperature of catalysis column are reacted；Reaction system is from 1#Leave 1 in catalysis column top#Column is catalyzed to enter
2#Head tank；2#Head tank comes from 1#The material and metered hydramine for being catalyzed column are sufficiently mixed (hydramine and original dichloro
Propane molar ratio is 1:1~10), under the effect of gravity, mixed solution is from 2#Head tank enters 2#Catalysis column bottom enters back into 2#
It is catalyzed in column, catalysis reaction is completed under the conditions of 55~90 DEG C, reaction mass is from 2#Reaction column is left into 3 in catalysis column top#It is high
Position slot.3#(new hydramine and the original dichloropropane molar ratio of being added is 1 to the metered hydramine of head tank:1~10), and from 2#
Be catalyzed column material be uniformly mixed, mixed solution under the effect of gravity, from 3#Head tank enters 3#It is catalyzed column bottom, again from 3#It urges
Change column bottom and enters 3#It is catalyzed in column, 3#It is catalyzed in column and is catalyzed reaction under the conditions of 65~100 DEG C, reaction product is from 3#It is catalyzed column
It leaves reaction column and enters product slot in top.When product tank liquor position reaches 3/4ths, liquid level triggering starting vacuum system is automatic to close
Product slot inlet valve and products export valve are closed, after deviating from low boiling component, closes vacuum system, outlet valve is opened and obtains final produce
Object.Low boiling component refers to that boiling point is lower than other components of final goal product.
In three sections of catalysis reactions, reaction system maintains micro-positive pressure.1#It is catalyzed column and controls 45~80 DEG C of reaction temperature, realize and produce
Object pre-reaction；2#It is catalyzed column and controls 55~90 DEG C of reaction temperature, complete most of raw material reaction；3#It is catalyzed column and controls reaction temperature
65~100 DEG C, raw material reaction is completed, product polyol amine is generated.The product of production carries out foam performance test.Three catalysis columns
Interior catalytic temperature gradually rises, i.e., and 1#It is catalyzed column reaction temperature<2#It is catalyzed column reaction temperature<3#It is catalyzed column reaction temperature.
Embodiment 1
Coconut husk charcoal is roasted into 6h in 300 DEG C of nitrogen atmosphere, the sodium hydrate aqueous solution of 7mol/L is used to impregnate 6h after cooling,
It is distilled after filtering water washing 4 times, after 120 DEG C of dry 6h, impregnates 8h with the aqueous solution of nitric acid of 7mol/L, distill water washing coconut husk charcoal
It is spare that 6h is roasted in 3 times, 120 DEG C of dry 6h after filtering, 300 DEG C.
The particle coconut husk charcoal and sodium hydroxide and lanthanum nitrate that processing is completed are according to mass ratio 100:5:1, sodium hydroxide
And lanthanum nitrate is made into mixed solution, excessively dipping absorption 10h, 120 DEG C of dry 8h are placed on horse boiling to coconut husk charcoal under stirring
Furnace, 350 DEG C of roasting 8h of nitrogen atmosphere, so that sodium hydroxide and lanthanum nitrate melting penetrate into active carbon duct and graphite linings
Between, it is bonded with particle coconut carbon surface carbon or group chemical, obtains solid super basic catalyst, filling is packed into catalysis after screening
Column.
Embodiment 2
1#Head tank, hydramine and dichloropropane in molar ratio 1:After 1 metering is mixed to form uniform solution, in gravity
Under, it is adjusted to 1000mL/min flow velocity, from 1#It is catalyzed column bottom and enters 1#It is catalyzed column, 60 DEG C of column temperature of control is reacted；Reactant
System leaves 1 from catalysis column top#Column enters 2#Head tank；2#Head tank comes from 1#The material of column is filled with metered hydramine
Dividing mixing, (hydramine is 1 with original dichloropropane molar ratio:2), under the effect of gravity, mixed solution is from 2#Column bottom is catalyzed to enter
2#It is catalyzed column, catalysis reaction is completed under the conditions of 70 DEG C, reaction mass leaves reaction column into 3 from catalysis column top#Head tank.
3#(hydramine is 1 with original dichloropropane molar ratio to the metered hydramine of head tank:2), and from 2#The material mixing of column is equal
It is even, solution under the effect of gravity, from 3#Column bottom enters 3#Be catalyzed column, in column under the conditions of 80 DEG C be catalyzed reaction, reaction product from
It leaves reaction column and enters product slot in catalysis column top.When product tank liquor position reaches 3/4ths, liquid level triggering starting vacuum system,
Product slot inlet valve and products export valve is automatically closed, after deviating from low boiling component, closes vacuum system, opens outlet valve and obtains
Product.Tail gas and product detection, dichloropropane conversion ratio 100.0%.
Embodiment 3
1#Head tank, hydramine and dichloropropane in molar ratio 1:After 2 meterings are mixed to form uniform solution, in gravity
Under, flow 1200mL/min flow velocity is adjusted, from 1#It is catalyzed column bottom and enters 1#It is catalyzed column, 60 DEG C of column temperature of control is reacted；Reaction
System leaves 1 from catalysis column top#Column enters 2#Head tank；2#Head tank comes from 1#The material of column and metered hydramine
It is sufficiently mixed that (hydramine and original dichloropropane molar ratio are 1:1), under the effect of gravity, mixed solution is from 2#Be catalyzed column bottom into
Enter 2#It is catalyzed column, catalysis reaction is completed under the conditions of 70 DEG C, reaction mass leaves reaction column into 3 from catalysis column top#It is high-order
Slot.3#(hydramine is 1 with original dichloropropane molar ratio to the metered hydramine of head tank:2), and from 2#The material of column is mixed
Close uniformly, solution under the effect of gravity, from 3#Column bottom enters 3#It is catalyzed column, is catalyzed reaction under the conditions of 80 DEG C in column, reaction produces
Object leaves reaction column from catalysis column top and enters product slot.When product tank liquor position reaches 3/4ths, liquid level triggering starting vacuum
Product slot inlet valve and products export valve is automatically closed in system, after deviating from low boiling component, closes vacuum system, opens outlet
Valve obtains product.Tail gas and product detection, dichloropropane conversion ratio 98.2%.
Embodiment 4
1#Head tank, hydramine and dichloropropane in molar ratio 1:After 2 meterings are mixed to form uniform solution, in gravity
Under, flow 1200mL/min flow velocity is adjusted, from 1#It is catalyzed column bottom and enters 1#It is catalyzed column, 60 DEG C of column temperature of control is reacted；Reaction
System leaves 1 from catalysis column top#Column enters 2#Head tank；2#Head tank comes from 1#The material of column and metered hydramine
It is sufficiently mixed that (hydramine and original dichloropropane molar ratio are 1:2), under the effect of gravity, mixed solution is from 2#Be catalyzed column bottom into
Enter 2#It is catalyzed column, catalysis reaction is completed under the conditions of 70 DEG C, reaction mass leaves reaction column into 3 from catalysis column top#It is high-order
Slot.3#(hydramine is 1 with original dichloropropane molar ratio to the metered hydramine of head tank:1), and from 2#The material of column is mixed
Close uniformly, solution under the effect of gravity, from 3#Column bottom enters 3#It is catalyzed column, is catalyzed reaction under the conditions of 80 DEG C in column, reaction produces
Object leaves reaction column from catalysis column top and enters product slot.When product tank liquor position reaches 3/4ths, liquid level triggering starting vacuum
Product slot inlet valve and products export valve is automatically closed in system, after deviating from low boiling component, closes vacuum system, opens outlet
Valve obtains product.Tail gas and product detection, dichloropropane conversion ratio 97.6%.
Embodiment 5
1#Head tank, hydramine and dichloropropane in molar ratio 1:After 2 meterings are mixed to form uniform solution, in gravity
Under, flow 1500mL/min flow velocity is adjusted, from 1#It is catalyzed column bottom and enters 1#It is catalyzed column, 70 DEG C of column temperature of control is reacted；Reaction
System leaves 1 from catalysis column top#Column enters 2#Head tank；2#Head tank comes from 1#The material of column and metered hydramine
It is sufficiently mixed that (hydramine and original dichloropropane molar ratio are 1:1), under the effect of gravity, mixed solution is from 2#Be catalyzed column bottom into
Enter 2#It is catalyzed column, catalysis reaction is completed under the conditions of 80 DEG C, reaction mass leaves reaction column into 3 from catalysis column top#It is high-order
Slot.3#(hydramine is 1 with original dichloropropane molar ratio to the metered hydramine of head tank:2), and from 2#The material of column is mixed
Close uniformly, solution under the effect of gravity, from 3#Column bottom enters 3#It is catalyzed column, is catalyzed reaction under the conditions of 80 DEG C in column, reaction produces
Object leaves reaction column from catalysis column top and enters product slot.When product tank liquor position reaches 3/4ths, liquid level triggering starting vacuum
Product slot inlet valve and products export valve is automatically closed in system, after deviating from low boiling component, closes vacuum system, opens outlet
Valve obtains product.Tail gas and product detection, dichloropropane conversion ratio 100.0%.Invention described above embodiment, not
Constitute limiting the scope of the present invention.It is any within the spirit and principles in the present invention made by modification, equivalent replacement and
Improve etc., it should be included within claims of the invention.
Claims (8)
1. a kind of preparation method of polyhydric alcohol amine, includes the following steps：
Step 1：Catalyst preparation
It by the roasting of particle cocoanut active charcoal, alkali cleaning, pickling, then dries, later by particle cocoanut active charcoal, alkali or alkaline oxygenated
Object and rare earth element, which are uniformly mixed, to be placed in crucible, is placed in nitrogen atmosphere muffle furnace, so that the melting of alkali, rare earth element is seeped
It penetrates between active carbon duct and carbon-coating, interacts with particle cocoanut active charcoal surface group, uniform solid phase is formed, after sieving
It is packed into column packed with catalyst, it is spare；
Step 2：Processing route
1 is added after dichloropropane and hydramine metering#The uniform solution that head tank, dichloropropane and hydramine are formed is under the effect of gravity
From 1#It is catalyzed column bottom and enters 1#It is catalyzed column, after being reacted under the action of catalyst, from 1#Leave 1 in catalysis column top#It is catalyzed column
Into 2#Head tank, 2#It is sufficiently mixed in head tank with metered hydramine；Again from 2#It is catalyzed column bottom and enters 2#Catalysis
Column, after catalyst effect, from 2#Leave 2 in catalysis column top#It is catalyzed column and enters 3#Head tank, 3#In head tank again with
The hydramine of addition mixes；Again from 3#It is catalyzed column bottom and enters 3#It is catalyzed column, after carrying out catalysis reaction under the action of catalyst, from 3#
Leave 3 in catalysis column top#Catalysis column enters product slot；Product slot obtains after deviating from low boiling component under vacuum system drive
Final product.
2. a kind of preparation method of polyhydric alcohol amine according to claim 1, which is characterized in that in step 1, coconut husk is living
Property charcoal roast 3~6h in 250~350 DEG C of nitrogen atmosphere, it is cooling after with the sodium hydroxide or potassium hydroxide water of 1~10mol/L
Solution impregnates 1~10h, distills after filtering water washing 2~6 times, after 110~150 DEG C of dry 3~12h, then with 1~10mol/L's
Aqueous solution of nitric acid impregnates 1~12h, is then washed with distilled water filtered cocoanut active charcoal 2~6 times, 110~150 DEG C dry
Dry 3~12h.
3. a kind of preparation method of polyhydric alcohol amine according to claim 2, which is characterized in that in step 1, will roast,
Cocoanut active charcoal after alkali cleaning, pickling, drying process, sodium hydroxide perhaps potassium hydroxide and lanthanum nitrate or cesium nitrate, is placed in
Muffle furnace, 250~550 DEG C of roastings in nitrogen atmosphere, so that the passing through of group of alkali, rare earth element and coconut activated carbon surface
It learns bond to close, obtains solid base catalyst, be fitted into catalysis column, it is spare.
4. a kind of preparation method of polyhydric alcohol amine according to claim 1, which is characterized in that in step 2, be additionally provided with
Following steps：Hydramine and dichloropropane are according to molar ratio 1:1 is added after 1~10 metering#Head tank, 1#Shape is mixed in head tank
After uniform solution, from 1#A or 1#B is catalyzed column bottom and enters 1#A or 1#B is catalyzed column, or enters 1 simultaneously#A and 1#B is catalyzed column,
After carrying out catalysis reaction under the action of catalyst, from 1#Catalysis column top exits into 2#Head tank, 2#From 1 in head tank#It urges
Change the material that column top is left to be sufficiently mixed with metered hydramine, hydramine and 1#The dichloropropane of the original addition of head tank rubs
You are than being 1:1~10；Under the effect of gravity, 2#The solution being uniformly mixed in head tank is from 2#It is catalyzed column bottom and enters 2#A or 2#b
It is catalyzed column or 2#A and 2#B is catalyzed column, after catalyst effect, from 2#Catalysis column top exits into 3#Head tank；?
3#From 2 in head tank#The material that catalysis column top is left is sufficiently mixed with metered hydramine, hydramine and 1#Head tank is initial
The dichloropropane molar ratio of addition is 1:1~10；Under the effect of gravity, 3#The solution being uniformly mixed in head tank is from 3#It is catalyzed column
Bottom enters 3#A or 3#B is catalyzed column or 3#A and 3#B is catalyzed column, after catalyst reaction, from 3#It leaves catalysis column top
3#Catalysis column enters product slot；Product tank liquor position is at 3/2nds to four/3rds, liquid level triggering starting vacuum system, abjection
Product is obtained after low boiling component；Wherein, 1#Being catalyzed column includes 1 be arranged in parallel#a、1#B is catalyzed column；2#Being catalyzed column includes parallel connection
2 be arranged#a、2#B is catalyzed column；3#Being catalyzed column includes 3 be arranged in parallel#a、3#B is catalyzed column.
5. a kind of preparation method of polyhydric alcohol amine according to claim 1, which is characterized in that 1#Being catalyzed column reaction temperature is
45~80 DEG C；2#55~90 DEG C of column reaction temperature of catalysis；3#65~100 DEG C of column reaction temperature of catalysis.
6. a kind of preparation method of polyhydric alcohol amine according to claim 1, it is characterised in that：The dichloropropane is 1,2- bis-
Chloropropane or 1,3- dichloropropane or 1,2- dichloropropane and 1,3- dichloropropane mixed solution.
7. a kind of preparation method of polyhydric alcohol amine according to claim 1, it is characterised in that：The hydramine isWherein R1, R2 CH3, CH3CH2, CH3CH2CH2,
CH3CH2CH2CH2,R1 is identical or different with R2.
8. a kind of preparation method of polyhydric alcohol amine described in -5 any one according to claim 1, it is characterised in that：It is prepared to urge
Agent is renewable after use, is recycled after regeneration.
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