CN109134278A - The preparation method of polyhydric alcohol amine - Google Patents
The preparation method of polyhydric alcohol amine Download PDFInfo
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- CN109134278A CN109134278A CN201811317681.9A CN201811317681A CN109134278A CN 109134278 A CN109134278 A CN 109134278A CN 201811317681 A CN201811317681 A CN 201811317681A CN 109134278 A CN109134278 A CN 109134278A
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- dichloropropane
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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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation methods of polyhydric alcohol amine, belong to chemical technology field, include the following steps: that raw material after pre-reaction, is transferred to heating pressurization in autoclave and completes to react in tube auger propulsion reactor；Continuous desalination non-wastewater discharge technique synthesis polyhydric alcohol amine is designed simultaneously.The present invention provides a kind of dichloropropane deep working method, solves the problems, such as that dichloropropane other application approach pollutes environment, belong to green chemical industry technique；The present invention provides a kind of polyhydric alcohol amine preparation method, and operating cost is low, high production efficiency, and product polyol amine molecule amount appropriateness, active functionality is high, is suitble to industrialized production.
Description
Technical field
The present invention relates to a kind of preparation methods of polyhydric alcohol amine, belong to chemical technology field.
Background technique
Chlorohydrination produces a large amount of dichloropropanes of epoxychloropropane process by-product.Dichloropropane obtains the third two by aminating reaction
Amine, however dichloropropane aminating reaction pressure is high, risk is big, post-processes long flow path and generates a large amount of contaminated wastewater environment.Two
Under the action of catalyst, chlorination reaction generates tetrachloro-ethylene and carbon tetrachloride, dichloropropane high temperature to chloropropane in 490 DEG C of air streams
Chlorallylene and 1- chloropropene are produced in decomposition；The chlorination and decomposition reaction condition are harsh, and equipment requirement is high.Dichloropropane hydrolysis system
Take propylene glycol handicraft product yield low, a large amount of Nacls of by-product, while generating a large amount of industrial wastewaters.In order to improve chlorohydrination production
The comprehensive benefit of propylene oxide reduces the consumption of raw materials of product propylene, and rationally processing is one using by-product dichloropropane
Anxious technical task leaved for development.
Summary of the invention
To solve the above-mentioned problems, the present invention provides a kind of preparation methods of polyhydric alcohol amine, using dichloropropane, hydramine
And catalyst continuously promotes reactor feed to tube auger after evenly mixing；After desalination, reaction system is in high temperature and pressure
Continue end reaction in tank reactor, obtains pure product after vacuum stripping, unreacting material and Water Cycle are extremely
Feed end continues to use, the preceding bottom salt discharge of blowing.
The present invention under catalyst (alkali) effect, carries out substitution reaction using dichloropropane and hydramine as raw material.Reaction equation is such as
Under:
R1 in formula, R2 CH3, CH3CH2, CH3CH2CH2,CH3CH2CH2CH2,In
It is one or several kinds of；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, by-product Nacl can continuously be discharged, and no wastewater discharge is fitted
Close industrialized production.
To achieve the goals above, the technical solution adopted by the present invention are as follows: a kind of preparation method of polyhydric alcohol amine, including such as
Lower step:
Step 1: pretreatment of raw material
Dichloropropane, hydramine and catalyst are proportionally mixed to form uniform sizing material, are added to tube auger propulsion
Reactor.
Step 2: technical process
The uniform sizing material that dichloropropane, hydramine and catalyst are formed is added to tube auger from feed opening and promotes reaction
Device, perhaps two chlorine are replaced one substitution polyhydric alcohol amine of generation or two taken by amine alcohols the one of dichloropropane at a set temperature
For polyhydric alcohol amine product, while substituted chlorine generates by-product Nacl.Since be less than can be with for solubility in water for sodium chloride
Arbitrary proportion is dissolved in the alkali of water, can during the reaction constantly by the water in control reaction process, i.e. adjusting alkali concentration
Salt is precipitated.Under the promotion that tube auger promotes reactor, the Nacl being precipitated in reaction process is promoted from tubular reactor
It is sent to salt collector (that is, salt is discharged from reaction system, into collector).Reaction system after desalination is in screw propulsion reactor
Under effect, it is sent into reaction kettle pressurization and is warming up to substituted fully reacting.In reaction kettle, vacuum extraction goes out unreacted dichloro third
Alkane and moisture are recycled to feed end (being re-used as raw material, be mixed to form uniform sizing material with hydramine and catalyst) continuation
It uses.Reaction product is packed after further filtering desalination.
Pass through control feed stock and catalyst proportion, reaction system non-wastewater discharge.
The dichloropropane is 1,2- dichloropropane or 1,3- dichloropropane or 1,2- dichloropropane and 1,3- bis-
Chloropropane mixed solution.
The hydramine is
Wherein R1, R2 CH3, CH3CH2, CH3CH2CH2,CH3CH2CH2CH2,R1 is identical or different with R2.
The by-product Nacl that designed technique can generate in continuous removal process, non-wastewater discharge.
Catalyst in the uniform sizing material is business liquid alkaline, perhaps make by oneself liquid alkaline perhaps business solid base or from
Solid base processed.Specifically, the uniform sizing material (when i.e. uniform sizing material underfill tube auger promotes reactor) is reacted the initial stage
Middle catalyst is business liquid alkaline or self-control liquid alkaline；After uniform sizing material promotes reactor full of tube auger, catalyst in raw material
It replaces with business solid base or self-control solid base (this is because after uniform sizing material promotes reactor full of tube auger, reacts
Vacuum extraction goes out unreacted dichloropropane and Water Cycle to feed end and uses in kettle, it is only necessary to solid catalyst be added i.e.
Can).
The screw propulsion reactor is that tube auger promotes reactor；The reaction temperature of screw propulsion reactor is arranged
It is 50~100 DEG C, 0.10~1.00m/min of flow velocity, 10.00~100.00rad/min of revolving speed.It receives screw propulsion reactor end
Reaction system (reaction system after desalination is obtained by salt collector desalination in screw propulsion reactor end) after collecting desalination
It is transferred to tank reactor；100~200 DEG C of reaction temperature in tank reactor, 50.00~200.00rad/ of mixing speed
Min, 1.00~5.00MPa of pressure.
After tank reactor fully reacting and pressure are stablized and reaction was completed, at 50~80 DEG C of temperature, vacuum degree 0.10~
It is stripped under the conditions of 0.50MPa, condensate circulation to feed end uses；Salt discharge blowing is (if anti-in screw propulsion after completing stripping
It answers unreacted in device complete, then will continue to fully reacting in tank reactor, this process also has salt to come out, so reaction kettle
Interior reaction terminates, and a small amount of salt that may be present to be also discharged after stripping, and blowing refers to that reaction product is collected).Stripping conditions: low temperature,
Band vacuum；Temperature height can polymerize, and product viscosity can become larger.
The preparation step of catalyst are as follows: by cocoanut active charcoal after roasting, alkali cleaning, pickling, drying process, sodium hydroxide or
Potassium hydroxide and lanthanum nitrate or cesium nitrate, are placed in muffle furnace, 250~550 DEG C of roastings in nitrogen atmosphere, so that alkali, dilute
The group of earth elements and coconut activated carbon surface obtains self-control solid base catalyst by chemical bonds, spare.
Compared with prior art, the invention has the advantages that: successful design continuous charging, successive reaction and
Automatic desalting system, unreacting material and moisture can be recycled to raw material after stripping the reaction was continued, and feed stock conversion is high, nothing
Discharge of wastewater, reaction process are environmentally protective；The degree of functionality of product can be with flexible modulation.
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 the uniform sizing material that Fig. 1 and 2, dichloropropane, hydramine and catalyst are formed, tubular type spiral shell is added to from feed opening
Rotation promotes reactor, and dichloropropane is replaced by amine alcohol at a set temperature, generates one and polyhydric alcohol amine and two is replaced to replace polyalcohol
Amine product, while generating by-product Nacl.Control catalyst concn is adjusted, salt is constantly precipitated in reaction process；In screw propulsion
Under the promotion of reactor, the Nacl of precipitation promotes reactor propulsion to be sent to salt collector from tube auger, and reaction system is discharged.
Reaction system after desalination is sent into reaction kettle (i.e. tank reactor) pressurization and is warming up to substituted fully reacting after being collected by filtration.?
In reaction kettle, vacuum extraction, which goes out unreacted dichloropropane and moisture and is recycled to feed end, to be continued to use, and product is further
It is packed after filtering desalination.
A kind of preparation method of polyhydric alcohol amine, including process are as follows:
By dichloropropane, hydramine according to molar ratio 1:1~4, dichloropropane and base catalyst according to equivalent proportion be 1:1~4,
It is mixed to form uniform sizing material, tube auger is added to from feed opening and promotes reactor.Tube auger promotes reactor setting reaction
50~100 DEG C of temperature；Promote 0.10~1.00m/min of linear velocity, 10.00~100.00rad/min of revolving speed.At a set temperature
One of dichloropropane perhaps two chlorine by amine alcohol replace generation one replace polyhydric alcohol amine or two replace polyhydric alcohol amine products,
By-product Nacl is generated simultaneously.
Under the promotion of screw propulsion reactor, the Nacl being precipitated in reaction process is promoted from tubular reactor and is sent to
Reaction system is discharged in salt collector.Tank reactor is collected by filtration in reaction system after desalination, at 100~200 DEG C of temperature；It stirs
50.00~200.00rad/min of speed is mixed, 1.00~5.00MPa of pressure is reacted to substituted fully reacting, and pressure is stablized
After terminate.It is stripped under the conditions of 50~80 DEG C of temperature, 0.10~0.50MPa of vacuum degree；Vacuum extraction goes out unreacted dichloro third
Alkane and moisture are recycled to feed end use.Inspection is packed after product filters desalination.
Pass through control feed stock and catalyst proportion, reaction system non-wastewater discharge.
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, obtained from alkaline catalyst.
Embodiment 2
Dichloropropane, diisopropanolamine (DIPA) and sodium hydroxide (48.0wt%) molar ratio 1:2:2, metering are mixed to form uniform molten
After liquid, tube auger is added and promotes reactor.Tube auger promotes reactor to set 80 DEG C of reaction temperature, linear advancement speed
0.50m/min.It reacts the salt generated and enters salt collector discharge reactor under the action of spiral propeller.Reaction after desalination
Tank reactor is collected by filtration in system, at 140 DEG C of temperature；Mixing speed 80.0rad/min, pressure 2.0MPa reacted to
Pressure terminates after stablizing.It is stripped under the conditions of 80 DEG C of temperature, vacuum degree 0.40MPa；Vacuum extraction go out unreacted light component and
Water is recycled to feed end use, and inspection (Fig. 3) is packed after product filters desalination, dichloropropane conversion ratio 98.2%.
Embodiment 3
Dichloropropane, diisopropanolamine (DIPA) and sodium hydroxide (48.0wt%) are pressed according to molar ratio 1:2:2, and metering is mixed to form
After uniform solution, tube auger is added and promotes reactor, after material is full of reactor, raw material proportioning is changed to dichloropropane, two
Isopropanolamine and sodium hydroxide (100.0wt%) molar ratio 1:2:2, tube auger promote reactor to set 70 DEG C of reaction temperature,
Linear advancement speed 0.40m/min.It reacts the salt generated and enters salt collector discharge reactor under the action of spiral propeller.
Tank reactor is collected by filtration in reaction system after desalination, at 130 DEG C of temperature；Mixing speed 90.0rad/min, pressure
2.0MPa terminates after being reacted to pressure stabilization.It is stripped under the conditions of temperature 70 C, vacuum degree 0.20MPa；Vacuum extraction goes out
Light component and water are recycled to feed end use.Inspection is packed after product filters desalination.Tail gas and product detection, dichloropropane turn
Rate 100.0%.
Embodiment 4
Dichloropropane, diisopropanolamine (DIPA) and sodium hydroxide (48.0wt%) molar ratio 1:2:2, metering are mixed to form uniform molten
Liquid is added tube auger and promotes reactor, and after material is full of reactor, raw material proportioning is changed to dichloropropane, diisopropanolamine (DIPA)
With sodium hydroxide (100.0wt%) molar ratio 2:3:3, tube auger promotes reactor to set 80 DEG C of reaction temperature, linear advancement
Speed 0.30m/min.It reacts the salt generated and enters salt collector discharge reactor under the action of spiral propeller.After desalination
Reaction system enters back into tank reactor after being further collected by filtration, at 140 DEG C of temperature；Mixing speed 90.0rad/min, pressure
1.5MPa reacted to pressure stablize (when fully reacting, the dichloropropane of vaporization returns to liquid phase from autoclave body gas phase, only there are
Air, thus pressure stablize) after terminate.It is stripped under the conditions of temperature 70 C, vacuum degree 0.10MPa；Vacuum extraction goes out light component
And water is recycled to feed end use.Inspection is packed after product filters desalination.Tail gas and product detection, dichloropropane conversion ratio
89.2%.
Embodiment 5
Dichloropropane, diisopropanolamine (DIPA) and self-control catalyst molar ratio 1:2:2 metering are mixed to form uniform sizing material and pipe are added
Formula screw propulsion reactor, tube auger promote reactor to set 80 DEG C of reaction temperature, linear advancement speed 0.30m/min.Instead
It answers rear catalyst to enter collector discharge reactor cycles under the action of spiral propeller to use.Except the reactant after catalyst
Tank reactor is collected by filtration in system, at 120 DEG C of temperature；Mixing speed 90.0rad/min, pressure 1.0MPa are reacted to pressure
Power terminates after stablizing.It is stripped under the conditions of temperature 60 C, vacuum degree 0.10MPa；Vacuum extraction goes out light component and water is recycled to
Feed end uses.Inspection is packed after product filtering.Tail gas and product detection, dichloropropane conversion ratio 100.0%.
The embodiments of the present invention described above are not intended to limit the scope of the present invention.It is any in the present invention
Spirit and principle within made modifications, equivalent substitutions and improvements etc., should be included in claim protection model of the invention
Within enclosing.
Claims (9)
1. a kind of preparation method of polyhydric alcohol amine, which comprises the steps of:
Step 1: pretreatment of raw material
Dichloropropane, hydramine and catalyst are proportionally mixed to form uniform sizing material；The catalyst is alkali；
Step 2: technical process
The uniform sizing material that dichloropropane, hydramine and catalyst are proportionally mixed to form is added to spiral from feed opening and pushes away
Into reactor；In the screw propulsion reactor of set temperature, the chlorine on dichloropropane is replaced by hydramine, generates polyhydric alcohol amine,
It is substituted the chlorine to get off and forms by-product salt；Under the promotion of screw propulsion reactor, the salt that is precipitated in reaction process is from spiral
It promotes to promote in reactor and is sent to salt collector, salt is discharged from reaction system；
Reaction system after desalination is sent into tank reactor pressurization and is warming up to fully reacting under the effect of screw propulsion reactor；
Vacuum extraction goes out unreacted dichloropropane and moisture and is recycled to feed end and continues to use again.
2. a kind of preparation method of polyhydric alcohol amine according to claim 1, it is characterised in that: the dichloropropane is 1,2-
Dichloropropane or 1,3- dichloropropane or 1,2- dichloropropane and 1, the mixed solution of 3- dichloropropane composition；The alcohol
Amine is
OrWherein R1, R2 CH3, CH3CH2, CH3CH2CH2,CH3CH2CH2CH2,One or more, R1 is identical or different with R2.
3. a kind of preparation method of polyhydric alcohol amine according to claim 1, which is characterized in that dichloropropane rubs with hydramine
You are than being 1:1~4；Dichloropropane and alkali equivalent ratio are 1:1~4.
4. a kind of preparation method of polyhydric alcohol amine according to claim 1 or 2, which is characterized in that the uniform sizing material
In catalyst be business liquid alkaline, perhaps make by oneself liquid alkaline perhaps business solid base or self-control solid base.
5. a kind of preparation method of polyhydric alcohol amine according to claim 1 to 3, which is characterized in that reaction is initial
Catalyst is business liquid alkaline or self-control liquid alkaline in the uniform sizing material in stage；Reactor is promoted full of tube auger in uniform sizing material
Afterwards, catalyst replaces with business solid base or self-control solid base in raw material.
6. a kind of preparation method of polyhydric alcohol amine according to claim 1, which is characterized in that the screw propulsion reaction
Device is that tube auger promotes reactor；The reaction temperature of screw propulsion reactor is set as 50~100 DEG C, and flow velocity 0.10~
1.00m/min, 10.00~100.00rad/min of revolving speed.
7. a kind of preparation method of polyhydric alcohol amine according to claim 1, which is characterized in that screw propulsion reactor end
Reaction system after collecting desalination is transferred to tank reactor；100~200 DEG C of reaction temperature in tank reactor, stirring speed
Spend 50.00~200.00rad/min, 1.00~5.00MPa of pressure.
8. a kind of preparation method of polyhydric alcohol amine according to claim 1, which is characterized in that reaction was completed for tank reactor
Afterwards, it is stripped under the conditions of 50~80 DEG C of temperature, 0.10~0.50MPa of vacuum degree, condensate circulation to feed end uses；Complete vapour
Mention rear salt discharge blowing.
9. a kind of preparation method of polyhydric alcohol amine according to claim 1, which is characterized in that by roasting, alkali cleaning, pickling,
Cocoanut active charcoal after 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 group of alkali, rare earth element and coconut activated carbon surface passes through chemical bonds,
Self-control solid base catalyst is obtained, it is spare.
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| US4493909A (en) * | 1981-06-25 | 1985-01-15 | Bayer Aktiengesellschaft | Poly-N,N-hydroxyalkylamides of polybasic carboxylic acids and a process for the production thereof |
| US4937269A (en) * | 1986-08-29 | 1990-06-26 | University Of Akron | Macrophage stimulation by homologs or analogs of quadrol |
| RO102817A2 (en) * | 1988-12-16 | 1991-12-09 | Inst De Medicina Si Farmacie I | Hydroxyalkyl-homopiperazines derivatives of theocin and producing |
| CN1160311C (en) * | 1998-05-28 | 2004-08-04 | 埃姆斯化学公司 | Process for preparing beta-hydroxyalkylamides |
| CN102199467A (en) * | 2011-04-06 | 2011-09-28 | 修建东 | Preparation method of Alpha-donamide aqueous antirust lubricant |
| CN102875405A (en) * | 2012-10-24 | 2013-01-16 | 南京工业大学 | Polyol of basic amino acid or ester thereof, preparation and application thereof |
-
2018
- 2018-11-07 CN CN201811317681.9A patent/CN109134278B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4493909A (en) * | 1981-06-25 | 1985-01-15 | Bayer Aktiengesellschaft | Poly-N,N-hydroxyalkylamides of polybasic carboxylic acids and a process for the production thereof |
| US4937269A (en) * | 1986-08-29 | 1990-06-26 | University Of Akron | Macrophage stimulation by homologs or analogs of quadrol |
| RO102817A2 (en) * | 1988-12-16 | 1991-12-09 | Inst De Medicina Si Farmacie I | Hydroxyalkyl-homopiperazines derivatives of theocin and producing |
| CN1160311C (en) * | 1998-05-28 | 2004-08-04 | 埃姆斯化学公司 | Process for preparing beta-hydroxyalkylamides |
| CN102199467A (en) * | 2011-04-06 | 2011-09-28 | 修建东 | Preparation method of Alpha-donamide aqueous antirust lubricant |
| CN102875405A (en) * | 2012-10-24 | 2013-01-16 | 南京工业大学 | Polyol of basic amino acid or ester thereof, preparation and application thereof |
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