Background technology
(be called for short peregal-O) is a kind of nonionogenic tenside commonly used to high-carbon fatty alcohol polyoxyethylene ether, soluble in water, has good level dyeing, diffusion, infiltration, emulsification, boiling-off, washs, strips and wettability, is widely used in dyeing.Other can be used as emulsifying agent, wetting Agent for Printing Inks, matrix etc. and is widely used in daily-use chemical industry industries such as makeup.
The following reaction of the general employing of the production method of peregal-O at present:
In the epoxyethane ring-expansion polymerization process, along with the variation of temperature of reaction and oxyethane import volume, simultaneously some unavoidable side reactions also can take place, the by product of generation has 1,4-diox (abbreviation diox) makes product have certain irritating smell.
1, the 4-diox (dioxane) claim dioxane or dioxane again, and colourless liquid has peculiar smell slightly, density 1.0329, and specific refractory power 1.4175, fusing point is 11 ℃, 101.1 ℃ of boiling points with water and many immiscible organic solvents, are a kind of harmful materials.Owing to use peregal-O in a large number at cosmetic field, it directly contacts with human body, and the content of diox is controlled in universal demand strictness in used for cosmetic peregal-O product at present in the world, and general requirement is below 100ppm.
In peregal-O production process, through a large amount of facts have proved, adopt some conversion units, by strict controlled polymerization temperature, pressure and oxyethane import volume, can reduce the generation that generates the diox side reaction greatly, but above-mentioned control requires harsh, causes throughput to descend, and exists the De diox still can't reach the super low loading requirement in the finished product simultaneously.
Summary of the invention
The technical issues that need to address of the present invention provide in a kind of production process of high-carbon fatty alcohol polyoxyethylene ether deviates from 1, the technology of 4-diox, it mainly is to solve existing in prior technology to deviate from 1, the control of 4-diox requires harsh, cause throughput to descend, exist the De diox still can't reach the technical problem that super low loading requires grade simultaneously in the finished product.
Above-mentioned technical problem of the present invention is mainly solved by following technical proposals:
Deviate from 1 in a kind of production process of high-carbon fatty alcohol polyoxyethylene ether of the present invention, the technology of 4-diox is characterized in that:
A. utilize the high pressure polymerisation reactor, sodium methylate is a catalyzer, and polyreaction obtains the high-carbon fatty alcohol polyoxyethylene ether raw product, sucks Glacial acetic acid in raw product, guarantees that neutralization back pH value is in 6.0~7.0 scopes;
B. suck deionized water in reactor, the weight percent that deionized water accounts for the raw product amount is 5.0~8.0%, fully stirs, and makes mixing of materials even;
C. heat up, under the material circulation spray condition, De diox and moisture content form azeotrope in the material, are deviate from by vacuum in vacuum decompression and still;
D. deviate from De diox and moisture content azeotrope and enter vacuum cooler-condenser and collect, be disposed to sewage lagoon and handle, product detect diox content up to standard after, heat up, continue vacuum removal moisture content, be lower than 1.0% to the moisture determination value, can carry out finished product cooling, slice packaging.
Adopting Press outer circulation spray polymerization conversion unit and sodium methylate is catalyzer, can reduce the generation that generates the diox side reaction greatly, high-carbon fatty alcohol polyoxyethylene ether raw product pH value is adjusted to 6.0~7.0, add an amount of water, keep 85~95 ℃ of temperature of charge, in the still vacuum degree control-0.035~-0.085MPa, utilize the spray effect of Press outer circulation spray polymerization conversion unit, in time deviate to generate the azeotrope that De diox and moisture content form.
As preferably, add following steps between described step c and the d: reduce vacuum tightness in the still, suck deionized water once more, the weight percent that deionized water accounts for the raw product amount is 8.0~10.0%, fully stirs; Temperature of charge in the control still continues under the material circulation spray condition, to deviate from residual diox and moisture content and form azeotrope in vacuum decompression and still.Handle by twice decompression azeotropic, the final diox residual content of product is lower than 100ppm substantially, and Special Circumstances do not reach standard, and the azeotropic that can reduce pressure is for the third time handled, and treatment process is with for the second time identical.
As preferably, more than the step that adds between step c and the d is implemented once.
As preferably, described high pressure polymerisation reactor is a Press outer circulation spray polymerization conversion unit.
As preferably, the time of stirring among the described step b is 30~50min.
As preferably, heating up among the described step c makes that temperature of charge is 85~95 ℃ in the still, in the still vacuum degree control-0.035~-0.085MPa.
As preferably, after described steps d Zhong diox content is up to standard, be warmed up to 105~115 ℃, continue vacuum removal moisture content
As preferably, the vacuum tightness in the described reduction still to-below the 0.085MPa.
As preferably, the time of described stirring is 30~50min.
As preferably, in the described control still temperature of charge in 85~95 ℃ of scopes, thereby deviate from residual diox and moisture content forms azeotrope.
Therefore, the present invention has by not transforming existing high-carbon fatty alcohol polyoxyethylene ether production unit, under the situation of not additional investment, by controlling raw product pH value, amount of water, removing technologies such as temperature, vacuum tightness, under Press outer circulation polymerization equipment spray condition, can make product De diox impurity obtain splendid removing, characteristics such as it is simple to have technology, and production cost is low.
Embodiment
Below by embodiment, technical scheme of the present invention is described in further detail.
Embodiment 1: deviate from 1 in a kind of production process of high-carbon fatty alcohol polyoxyethylene ether of this example, the technology of 4-diox the steps include:
A. adopting Press outer circulation spray polymerization conversion unit and sodium methylate is that catalyzer makes the high-carbon fatty alcohol polyoxyethylene ether raw product, and regulating pH value with Glacial acetic acid is 6.5;
B. suck the deionized water of raw product amount 5.5% (weight ratio), 30min is stirred in circulation;
C. be warming up to 90 ℃, maintain under this state of temperature, open vacuum unit, control vacuum tightness-0.035~-the 0.085MPa scope in, under decompression spray art condition, remove diox-moisture content azeotrope; Vacuum tightness reduces to-below the 0.085MPa, suck raw product amount 8.0% deionized water (weight ratio) once more, and 30min is stirred in circulation; Heat up temperature of charge in the control still at 90 ℃, vacuum tightness-0.035~-0.085MPa, continue to remove residual diox;
D. vacuum tightness is reduced to-0.085MPa, and it is 24ppm that sampling detects diox content, continues to be warming up to 110 ℃, and vacuum removal moisture content is extremely qualified, the slice packaging finished product, and final detection result diox content is 22ppm.
Embodiment 2: deviate from 1 in a kind of production process of high-carbon fatty alcohol polyoxyethylene ether of this example, the technology of 4-diox the steps include:
A. adopting Press outer circulation spray polymerization conversion unit and sodium methylate is that catalyzer makes the high-carbon fatty alcohol polyoxyethylene ether raw product, and regulating high-carbon fatty alcohol polyoxyethylene ether raw product pH value with Glacial acetic acid is 6.2;
B. suck the deionized water of raw product amount 6.0% (weight ratio), 30min is stirred in circulation;
C. be warming up to 88 ℃, maintain under this state of temperature, open vacuum unit, control vacuum tightness-0.035~-the 0.085MPa scope in, under decompression spray art condition, remove diox-moisture content azeotrope.Vacuum tightness is reduced to below the 0.085MPa, sucks raw product amount 10.0% deionized water (weight ratio) once more, and 30min is stirred in circulation; Heat up temperature of charge in the control still at 88 ℃, vacuum tightness-0.035~-0.085MPa, continue to remove residual diox;
D. vacuum tightness is reduced to-0.085MPa, and it is 32ppm that sampling detects diox content, continues to be warming up to 110 ℃, and vacuum removal moisture content is extremely qualified, the slice packaging finished product, and final detection result diox content is 29ppm.
Embodiment 3: deviate from 1 in a kind of production process of high-carbon fatty alcohol polyoxyethylene ether of this example, the technology of 4-diox the steps include:
A. adopting Press outer circulation spray polymerization conversion unit and sodium methylate is that catalyzer makes the high-carbon fatty alcohol polyoxyethylene ether raw product, and regulating thick ether goods pH value with Glacial acetic acid is 6.4;
B. suck the deionized water of raw product amount 5.0% (weight ratio), 30min is stirred in circulation;
C. be warming up to 92 ℃, maintain under this state of temperature, open vacuum unit, control vacuum tightness-0.035~-the 0.085MPa scope in, under decompression spray art condition, remove diox-moisture content azeotrope; Vacuum tightness reduces to-below the 0.085MPa, suck raw product amount 8.0% deionized water (weight ratio) once more, and 30min is stirred in circulation.Heat up temperature of charge in the control still at 88 ℃, vacuum tightness-0.035~-0.085MPa, continue to remove residual diox;
D. vacuum tightness is reduced to-0.085MPa, and it is 42ppm that sampling detects diox content, continues to be warming up to 110 ℃, and vacuum removal moisture content is extremely qualified, the slice packaging finished product, and final detection result diox content is 41ppm.
Embodiment 4: deviate from 1 in a kind of production process of high-carbon fatty alcohol polyoxyethylene ether of this example, the technology of 4-diox the steps include:
A. adopting Press outer circulation spray polymerization conversion unit and sodium methylate is that catalyzer makes the high-carbon fatty alcohol polyoxyethylene ether raw product, and regulating thick ether goods pH value with Glacial acetic acid is 6.1;
B. suck the deionized water of raw product amount 7.5% (weight ratio), 30min is stirred in circulation;
C. be warming up to 90 ℃, maintain under this state of temperature, open vacuum unit, control vacuum tightness-0.035~-the 0.085MPa scope in, under decompression spray art condition, remove diox-moisture content azeotrope.Vacuum tightness reduces to-below the 0.085MPa, suck raw product amount 10.0% deionized water (weight ratio) once more, and 30min is stirred in circulation; Heat up temperature of charge in the control still at 93 ℃, vacuum tightness-0.035~-0.085MPa, continue to remove residual diox;
D. vacuum tightness is reduced to-0.085MPa, and it is 19ppm that sampling detects diox content, continues to be warming up to 110 ℃, and vacuum removal moisture content is extremely qualified, the slice packaging finished product, and final detection result diox content is 19ppm.
Embodiment 5: deviate from 1 in a kind of production process of high-carbon fatty alcohol polyoxyethylene ether of this example, the technology of 4-diox the steps include:
A. adopting Press outer circulation spray polymerization conversion unit and sodium methylate is that catalyzer makes the high-carbon fatty alcohol polyoxyethylene ether raw product, and regulating thick ether goods pH value with Glacial acetic acid is 6.5;
B. suck the deionized water of raw product amount 5.5% (weight ratio), 30min is stirred in circulation;
C. be warming up to 90 ℃, maintain under this state of temperature, open vacuum unit, control vacuum tightness-0.035~-the 0.085MPa scope in, under decompression spray art condition, remove diox-moisture content azeotrope.Vacuum tightness reduces to-below the 0.085MPa, suck raw product amount 8.0% deionized water (weight ratio) once more, and 30min is stirred in circulation; Heat up temperature of charge in the control still at 90 ℃, vacuum tightness-0.035~-0.085MPa, continue to remove residual diox;
D. vacuum tightness is reduced to-0.085MPa, and it is 24ppm that sampling detects diox content, continues to be warming up to 110 ℃, and vacuum removal moisture content is extremely qualified, the slice packaging finished product, and final detection result diox content is 22ppm.
Embodiment 6: deviate from 1 in a kind of production process of high-carbon fatty alcohol polyoxyethylene ether of this example, the technology of 4-diox the steps include:
A. adopting Press outer circulation spray polymerization conversion unit and sodium methylate is that catalyzer makes the high-carbon fatty alcohol polyoxyethylene ether raw product, and regulating thick ether goods pH value with Glacial acetic acid is 6.7;
B. suck the deionized water of raw product amount 6.3% (weight ratio), 30min is stirred in circulation;
C. be warming up to 86 ℃, maintain under this state of temperature, open vacuum unit, control vacuum tightness-0.035~-the 0.085MPa scope in, under decompression spray art condition, remove diox-moisture content azeotrope; Vacuum tightness reduces to-below the 0.085MPa, suck raw product amount 8.5% deionized water (weight ratio) once more, and 30min is stirred in circulation.Heat up temperature of charge in the control still at 91 ℃, vacuum tightness-0.035~-0.085MPa, continue to remove residual diox;
D. vacuum tightness is reduced to-0.085MPa, and it is 39ppm that sampling detects diox content, continues to be warming up to 110 ℃, and vacuum removal moisture content is extremely qualified, the slice packaging finished product, and final detection result diox content is 37ppm.
Embodiment 7: deviate from 1 in a kind of production process of high-carbon fatty alcohol polyoxyethylene ether of this example, the technology of 4-diox the steps include:
A. adopting Press outer circulation spray polymerization conversion unit and sodium methylate is that catalyzer makes the high-carbon fatty alcohol polyoxyethylene ether raw product, and regulating thick ether goods pH value with Glacial acetic acid is 6.5;
B. suck the deionized water of raw product amount 5.1% (weight ratio), 30min is stirred in circulation;
C. be warming up to 93 ℃, maintain under this state of temperature, open vacuum unit, control vacuum tightness-0.035~-the 0.085MPa scope in, under decompression spray art condition, remove diox-moisture content azeotrope.Vacuum tightness reduces to-below the 0.085MPa, suck raw product amount 8.0% deionized water (weight ratio) once more, and 30min is stirred in circulation; Heat up temperature of charge in the control still at 89 ℃, vacuum tightness-0.035~-0.085MPa, continue to remove residual diox;
D. vacuum tightness is reduced to-0.085MPa, and it is 56ppm that sampling detects diox content, continues to be warming up to 110 ℃, and vacuum removal moisture content is extremely qualified, the slice packaging finished product, and final detection result diox content is 50ppm.