CN1389467A - Method for preparing phosphate - Google Patents
Method for preparing phosphate Download PDFInfo
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- CN1389467A CN1389467A CN 02121657 CN02121657A CN1389467A CN 1389467 A CN1389467 A CN 1389467A CN 02121657 CN02121657 CN 02121657 CN 02121657 A CN02121657 A CN 02121657A CN 1389467 A CN1389467 A CN 1389467A
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- phosphoric acid
- acid ester
- manufacture method
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- gas element
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Abstract
A process for easily and quickly preparing a phosphoric ester having reduced odor is provided. A process for preparing a phosphoric ester by contacting a phosphoric ester with at least one of an inert gas and steam at 100 DEG C to 160 DEG C in a packed tower; a process for preparing a phosphoric ester, comprising repeating a set of processes comprising (A) heating a phosphoric ester, and contacting the heated phosphoric ester with at least one of an inert gas and steam; and (B) cooling the phosphoric ester obtained in the step (A); a process for preparing a phosphoric ester, comprising adding water to a phosphoric ester, and distilling water from the phosphoric ester under reduced pressure; and a process for preparing a phosphoric ester, comprising reacting an organic hydroxy compound with a phosphorylation agent, while introducing an inert gas.
Description
Technical field
The invention relates to the manufacture method of phosphoric acid ester.In more detail, be about for example manufacture method of effective phosphoric acid ester in shampoo, washing composition, the agent of washing one's face, emulsifying agent etc.
Prior art
The phosphoric acid ester of organic hydroxy compounds (below be also referred to as " phosphoric acid ester ") is used in fields such as washing composition, emulsifying agent, fibre finish, rust-preventive agent, medical treatment product.Especially, have alkanolamine salts such as an alkali metal salt of sodium, potassium etc. of an alkyl phosphate of chain alkyl or triethylamine, have water-solublely, foaming power or washing force are good, and toxicity or skin irritation are low, are useful in the commodity that directly use in the human body of the shampoo or the agent of washing one's face etc. therefore.Cooperate under the situation of phosphoric acid ester in the commodity that in such a human body, directly use, a little less than the stink of this phosphoric acid ester, become important as quality,
React by phosphoric acid agents such as organic hydroxy compounds and Vanadium Pentoxide in FLAKES, Tripyrophosphoric acid, Phosphorus Oxychlorides and to make phosphoric acid ester.But in this phosphoric acid ester, unreacted organic hydroxy compounds or the by products such as alkene that generate in phosphorylation reaction exist as impurity.These impurity as have smelly composition often stink bring baneful influence, thereby need after reaction, be used to remove the complex process of smelly composition.
Deodour method as impurity such as removal organic hydroxy compounds has proposed to use solvent that phosphoric acid ester is recrystallized and has carried out isolating method (spy opens flat 11～No. 158193 communiques); Utilize basic cpd to make phosphoric acid ester form phosphate ester salt, use solvent in the organic layer extraction smelly composition is arranged, in the method (special fair 03-027558 communique) of water layer phosphoric acid extraction ester salt.
But these methods are used solvent in large quantities, therefore need the equipment of recovery solvent etc.In addition, carry out in the isolating method in recrystallizationization, the occasion that on phosphoric acid ester with alkyl distribution or addition mole number, has the phosphoric acid ester of distribution at the epoxide affixture, the alkyl of phosphoric acid ester and the distribution of epoxide addition change before and after handling, have to produce the possibility that goods cooperate the problem of going up, and can not avoid the loss of phosphoric acid ester to solvent.In addition, in using the extraction process of solvent, beyond extraction solvent, as demulsifying compound, lower alcohol necessitates, thereby reclaims solvent and become complicated, and it is big that the facility investment volume becomes.
As above, in the method for using solvent, productivity is low and the change of facility investment volume is big, therefore has the shortcoming that cost improves.
On the other hand,, film-type deodorization towers such as rotating thin film formula rapid steamer, wet-wall tower have been proposed to use, the method that contacts with rare gas element (comprising water vapor) (special public clear 62-025155 communique) as the deodour method that does not use solvent; And while being blown into the method (special fair 05-066958 communique) that water vapor carries out phosphating reaction.
But, using film-type deodorization towers such as rotating thin film formula rapid steamer, wet-wall tower, be blown into the occasion that rare gas element is removed smelly composition, compare with the size that device is all, the contact area of gas-liquid is little, so contact efficiency is low, employed rare gas element quantitative change is many, and it is big that device also becomes, so the change of facility investment volume is big, and cost uprises.In addition, water displacement or exhaust quantitative change are many, and processing cost also uprises.
In addition, being blown in phosphating reaction under the situation of water vapor, is that Vanadium Pentoxide in FLAKES or the Tripyrophosphoric acid with phosphoric acid agent of tetra-sodium key decomposes by water vapor, and the worry of obstruction and organic hydroxy compounds reaction is arranged.Because this, unreacted organic hydroxy compounds quantitative change is many, and stink is brought baneful influence.
Therefore, wish exploitation can lower easily in phosphoric acid ester residual have smelly composition, can be economical and make the industrially preparing process of the few phosphoric acid ester of foul smell effectively.
Summary of the invention
The present invention is a problem with the method for can be easily and making the few phosphoric acid ester of foul smell rapidly.
That is, the invention relates to
(1) in packed tower, makes the manufacture method of the phosphoric acid ester that 100～160 ℃ phosphoric acid ester contacts with rare gas element and/or water vapor;
(2) (A) behind the heated phosphoric ester, make rare gas element/or process of contacting with this phosphoric acid ester of water vapor, and
(B) make the phosphoric acid ester that in process (A), obtains carry out the manufacture method of the phosphoric acid ester that the refrigerative process carries out repeatedly;
(3) in phosphoric acid ester, add entry, under reduced pressure distillate the manufacture method of the phosphoric acid ester of water; And
(4) when organic hydroxy compounds and phosphoric acid agent being reacted make phosphoric acid ester, import rare gas element, the manufacture method of the phosphoric acid ester of reacting.
As the phosphoric acid ester of using in the present invention, it is the phosphoric acid ester of organic hydroxy compounds, can enumerate a kind or 2 kinds of combinations, the phosphoric acid ester that obtains by reaction with phosphoric acid agents such as organic hydroxy compounds and Vanadium Pentoxide in FLAKES, Tripyrophosphoric acid, former phosphoric acid, Phosphorus Oxychlorides.Among these, never pair such as hydrochloric acid gas generates, does not need special equipment angle to set out, and phosphoric acid agent of selecting in the group of being made up of former phosphoric acid, Tripyrophosphoric acid and Vanadium Pentoxide in FLAKES more than a kind and organic hydroxy compounds react and the phosphoric acid that obtains is the best.
Under situation about using as phosphoric acid agent with Vanadium Pentoxide in FLAKES and Tripyrophosphoric acid, usually, the viewpoint that generates from the pair of the stability that lowers the goods such as washing composition that use phosphoric acid ester raw material etc. being brought the former phosphoric acid of baneful influence and lower the viewpoint of bringing the pair of the phosphodiester of baneful influence to generate to detergency and consider, relative 1 mole of Vanadium Pentoxide in FLAKES (is scaled the value of 138 weight % by former phosphoric acid, in the occasion of Tripyrophosphoric acid, Tripyrophosphoric acid concentration is to remove 138 value as P
2O
5Suitable weight ratio.Below identical), the amount of water is 0.5～1.5 mole, preferably 1～3 mole of the amount of organic hydroxy compounds.
Phosphorylation reaction is preferably in formula (1):
((mole number of the organic hydroxy compounds of interpolation)+
(with P
2O
5NH
2O represents as phosphoric acid agent, contains nH
2The mole number of the water of O)) ÷
(phosphoric acid agent is transformed into P
2O
5Mole number) value of (1) under 2.8～3.1 condition, carry out above-mentioned phosphorylation reaction.Formula (1) is 3.0, the scale of phosphoric acid agent and organic hydroxy compounds and water is shown as and is the chemical theory amount, owing to be in numerical range as described above, can lower unreacted residual organic hydroxy compounds amount, and the advantage of the decomposition of the phosphoric acid ester that generates in the reaction of being suppressed at is arranged.The value of formula (1) preferably 2.9～3.0.
In phosphoric acid ester, usually as smelly composition is arranged, contain unreacted organic hydroxy compounds or from the compound of organic hydroxy compounds, also contain the by product that in phosphorylation reaction, generates etc.
In phosphoric acid ester under the situation of residual tetra-sodium key, the viewpoint of the stability when goods cooperate is considered, adds water in phosphoric acid ester, can make the hydrolysis of tetra-sodium key.The addition that is used for the water of hydrolysis has no particular limits, but the blistered viewpoint from the corrosion of gelation, equipment and deodorization treating processes is after this considered, moisture concentration in the phosphoric acid ester in the hydrolysis better is to become the following such amount of 10 weight %, being more preferably becomes the following such amount of 5 weight %, preferably becomes the following such amount of 3 weight %.In addition, consider that from the viewpoint that is hydrolyzed efficiently the moisture concentration in the phosphoric acid ester in the hydrolysis better is more than the 0.01 weight %, preferably more than the 0.1 weight %.Consider that from these viewpoints moisture concentration better is 0.01～10 weight %, is more preferably 0.1～5 weight %, preferably 0.1～3 weight %.
In addition, the condition of hydrolysis has no particular limits.For example, preferably carry out the hydrolysis about 0.1～10 hour at 60～120 ℃.
After the hydrolysis, the blistered viewpoint in the corrosion of slave unit and the deodorization treating processes is after this considered, the moisture concentration in the phosphoric acid ester can be dewatered to 3 weight %.
Organic hydroxy compounds is the organic compound with hydroxyl.As the example of organic hydroxy compounds, can enumerate saturated or undersaturated alcohol, its epoxide affixture (carbonatoms of epoxide: alcohol 2～4) etc. of straight chain or side chain.These organic hydroxy compounds can 1 kinds or are used as the mixture more than 2 kinds.In these organic hydroxy compounds, the alcohol that better is carbonatoms 6～30 reaches in this alcohol with 1～10 mole of polyoxyalkylene alkyl ether with the epoxide addition of carbonatoms 2～4 of average addition mole number, preferably the alcohol of carbonatoms 8～14 reaches in this alcohol with 2～5 moles of average addition mole numbers, especially with 2～4 moles of polyoxyalkylene alkyl ether with the epoxide addition of carbonatoms 2～4.As the example of organic hydroxy compounds, can enumerate undecyl alcohol and addition mole number thereof and be 3 ethylene oxide adduct, lauryl alcohol and addition mole number thereof is ethylene oxide adduct of 2 etc.
What is called said in this manual " rare gas element " means in attenuating have under the treatment condition of smelly composition, the gas that does not give baneful influence to the quality and the harvest yield of phosphoric acid ester.Can enumerate nitrogen, argon gas, helium, carbonic acid gas etc. as rare gas element.In these gases, preferentially select nitrogen and carbonic acid gas, more preferably select nitrogen.
To rare gas element and water vapour, little from easy condensation to the heat energy load of condenser, the angle that the load of exhaust system is little is set out the preferably water steam.
The ratio of the flow of rare gas element and/or water vapor and the flow of the phosphoric acid ester (flow (m of rare gas element and/or water vapor
3/ h)/flow (kg/h) of phosphoric acid ester) value, from the viewpoint of avoiding high vacuum to necessitate, and lower the usage quantity of rare gas element and/or water vapor and the viewpoint of yield is considered, better be 0.1～3, preferably 0.2～1.5.Moreover said in this manual " flow of rare gas element and/or water vapor " is in standard state, promptly temperature be 0 ℃, the value when pressure is 101.3kPa.
The attenuating process that smelly composition is arranged that rare gas element and/or water vapor contact with phosphoric acid ester from lowering the big angle of effect, is preferably under the decompression of 20kPa and carries out.In addition, from the load of pressure regulating equipment with there is the viewpoint that smelly composition lowers effect to consider, carry out under the decompression of 0.1～14kPa more fortunately, be preferably under the decompression of 1～7kPa and carry out.In addition, from the thermolysis of phosphoric acid ester with there is the viewpoint that smelly composition lowers effect to consider that temperature better is 100 ℃～160 ℃, preferably 120～140 ℃.
In the present invention, contact with rare gas element and/or water vapor, can access the phosphoric acid ester that smelly composition lowers by in packed tower, making 100～160 ℃ phosphoric acid ester.
So-called packed tower is meant the tower that portion within it fills.Packed tower is compared with wet-wall tower with rotating thin film formula rapid steamer, multistage tower, because every device volumetrical gas-to-liquid contact area is big, be used to lower the processing speed that smelly composition is arranged so can improve, therefore can make device self miniaturization, and therefore the driving part as rotating thin film formula rapid steamer is not considered all good from energy efficiency and maintenance aspect.
The filler that uses in packed tower is with manufacturings such as metal such as stainless steel, titanium, the anti-corrosion Langaloy of haas troy or potteries.In order to lower the pressure-losses in the tower, filler preferably has 90～99% porosity.
For filler, have no particular limits.Filler can use the filler that uses usually in rectifying tower.Its kind roughly is divided into 2 kinds.Wherein a kind of is regular packing, and another kind is irregular filler.As regular packing, can enumerate ス Le ザ-corporate system ス Le ザ-パ キ Application Network (trade(brand)name) or モ Application Star corporate system モ Application Star パ
Starキ Application Network (trade(brand)name) etc.As irregular filler, can enumerate Raschig ring or Bel's saddle type filler etc.These fillers can use separately separately, also can more than 2 kinds and use.In these fillers, consider preferably regular packing from aspects such as the easy to use and pressure-losses are little.
The feed speed of the phosphoric acid ester of supplying with to packed tower and the processing speed of handling the phosphoric acid ester of discharging the back from packed tower equate.The processing speed of the processing speed of packed tower and intermittent type rapid steamer in the past and rotating thin film formula drying machine compares with the corresponding volumetrical processing speed of the contact part of these devices.The volume of contact part means in rotating thin film formula drying machine, to mean the volume of the filling part of filling filler to deposit the volume of face as lateral cylindrical inside in packed tower.
Phosphoric acid ester contacts with rare gas element and/or the phosphoric acid ester during water vapour and the flow direction of rare gas element and/or water vapour can be the either directions of horizontal direction and vertical direction.In these flow directions, consider from the viewpoint that improves deodorization efficiency, preferably vertical direction.In addition, as the rare gas element of the flow direction of relative phosphoric acid ester and/or the flow direction of water vapour, can enumerate following current and adverse current.Consider from the viewpoint of the deodorising effect that improves rare gas element and/or water vapor, preferably adverse current.
True consider that from these flow direction of phosphoric acid ester and rare gas element and/or water vapor is vertical direction and adverse current preferably.In addition,, consider as not main viewpoint, preferably supply with phosphoric acid ester, supply rare gas element at the bottom of the tower of packed tower from the cat head of packed tower with power from utilizing freely falling of phosphoric acid ester in the packed tower that causes by gravity.
Can not determine entirely with contact conditions of phosphoric acid ester and rare gas element and/or water vapor etc. and different the duration of contact of phosphoric acid ester and rare gas element and/or water vapor.Usually, from the pyrolysated that suppresses phosphoric acid ester simultaneously, being used to lower remainingly has the amount of inert gas of smelly composition otherwise the viewpoint that increases considers that the duration of contact of phosphoric acid ester and rare gas element and/or water vapor is preferably about 1～30 minute.
In addition, from the foaming of phosphoric acid ester and depend on that the viewpoint of the material of equipment detritus considers that the moisture concentration in the phosphoric acid ester is preferably below the 3 weight %.
In addition, behind the heated phosphoric ester, can make the process that this phosphoric acid ester contacts with rare gas element and/or water vapor (below, be also referred to as process (A)) repeatedly, lowered the phosphoric acid ester that smelly composition is arranged in the process (A) and carried out refrigerative process (below, be also referred to as process (B)) with making.
So-called process (A) is to use the process that general gas-liquid contact apparatus can lower smelly composition.As contact device, except that above-mentioned packed tower, for example can enumerate rotating thin film formula rapid steamer, the wet-wall tower put down in writing in the special public clear 57-35595 communique, flow down the film type rapid steamer, use the intermittent type contact device that is blown into pipe, column plate laminar contact device, rising film type contact device etc.
In these contact devices, become unnecessary angle from special device, use is blown into the intermittent type contact device of pipe, even under the situation of using more full-bodied phosphoric acid ester, the rotating thin film formula rapid steamer that can efficient contacts with rare gas element well is small-sized, also can make the contact area of phosphoric acid ester and rare gas element and/or water vapor big, in addition, be more preferably and lower the packed tower that smelly composition is arranged that is comprised, preferably packed tower efficiently.
Phosphoric acid ester when phosphoric acid ester contacts with rare gas element and/or water vapor and the flow direction of rare gas element and/or water vapor can be any of horizontal flow and vertical current.In these flow directions, consider from the viewpoint that improves deodorization efficiency, preferably vertical current.In addition, as the rare gas element of the flow direction of relative phosphoric acid ester and/or the flow direction of water vapor, can enumerate following current and adverse current.Consider from the viewpoint of the deodorising effect that improves rare gas element and/or water vapor, preferably counter-current operation.
Consider that from these the fact flow direction of phosphoric acid ester and rare gas element and/or water vapor is vertical direction and adverse current preferably.In addition,, consider as not main viewpoint, preferably supply with phosphoric acid ester, supply rare gas element and/or water vapour at the bottom of the tower of packed tower from the cat head of packed tower with power from utilizing freely falling of phosphoric acid ester in the packed tower that causes by gravity.
In addition, the heated phosphoric ester, the temperature when phosphoric acid ester is contacted with rare gas element and/or water vapor from the thermolysis of phosphoric acid ester with there is the viewpoint that smelly composition lowers effect to consider, better is 100～160 ℃, preferably 120～140 ℃.
Pressure when phosphoric acid ester contacts with rare gas element and/or water vapor from the attenuating process that smelly composition is arranged that rare gas element and/or water vapor contact with phosphoric acid ester, lowers effect and becomes big angle and sets out, and is preferably under the following decompression of 20kPa and carries out.In addition, from the load of pressure regulating equipment and there is the viewpoint of the attenuating effect of smelly composition to consider, carry out under the decompression of 0.1～14kPa more fortunately, be preferably under the decompression of 1～7kPa and carry out.
The duration of contact of rare gas element and/or water vapor and phosphoric acid ester, with contact conditions of phosphoric acid ester and rare gas element and/or water vapor etc. and different, can not determine entirely.Usually, from suppressing the pyrolysated while of phosphoric acid ester, the viewpoint that being used in the amount that lowers the rare gas element that smelly one-tenth component is arranged contain and/or water vapor does not increase considers that better be 1～100 minute the duration of contact of phosphoric acid ester and rare gas element and/or water vapor, preferably 1～30 minute.
In this occasion, in rare gas element and water vapor, because condensing easily, little to the heat energy load of condensed device, since also little to the load of exhaust system, so water vapor is best.
In addition, from the foaming of phosphoric acid ester and depend on that the viewpoint of the material of equipment corrosion considers that the moisture concentration in the phosphoric acid ester is preferably below the 3 weight %.
The phosphoric acid ester cooling that then, in process (B), will contact with rare gas element and/or water vapor.
Consider from the pyrolysated viewpoint of abundant inhibition phosphoric acid ester, preferably use refrigerating unit as much as possible, promptly carry out the cooling of phosphoric acid ester in the outlet of contact device.For refrigerating unit, can use general heat exchanger.As refrigerating unit, for example can enumerate multitube, double hose, spiral, board-like refrigerating unit etc., can use any refrigerating unit, but from being the angle small-sized, that rate of heat exchange is good, preferably screw type refrigerating unit.
In order to suppress the thermolysis of phosphoric acid ester, the cooling temperature of phosphoric acid ester better is below 90 ℃, is more preferably below 80 ℃, preferably below 60 ℃.
The lower limit of cooling temperature is different with the kind of phosphoric acid ester, therefore can not determine entirely.
Phosphoric acid ester has the character of thickening sharp generally with the reduction of its temperature.Under the situation of the thickening that such a phosphoric acid ester takes place, in refrigerating unit or pressure increase, or heat exchanger effectiveness reduces, and then owing to stops up the danger that exists running to become difficulty.Put from this, the lower limit of cooling temperature preferably phosphoric acid ester can keep mobile temperature.
Temperature as the flowability that can keep phosphoric acid ester, different with the kind of organic hydroxy compounds, can not determine entirely, but the occasion of the phosphoric acid ester of the organic hydroxy compounds of the average 3 moles of additions of oxyethane in using the alcohol of carbonatoms 11 for example preferably is defined as 5 ℃.
Moreover, the cooling of necessary above phosphoric acid ester, from then process (A) the heat energy during heating aspect consideration, be inappropriate.
Make phosphoric acid ester be cooled to the needed time of temperature desired, have no particular limits, but consider from the pyrolysated viewpoint of abundant inhibition phosphoric acid ester, short more as much as possible good more.The methods that increase as the heat transfer area that with the short period of time temperature of phosphoric acid ester is reduced to the method for temperature desired, can enumerates the method for temperature that reduces cooling agent, makes heat exchanger etc., these methods can be used separately or can and use.
Then, the occasion that enters receiver in the phosphoric acid ester of supplying with contact device, after chilled phosphoric acid ester being recovered to and supplying with in the receiver of the receiver difference that the phosphoric acid ester of contact device enters, can carry out to be called the periodical operation of supplying with said process (A) again, in addition, also the phosphoric acid ester by contact device can be recovered on one side in the receiver that the phosphoric acid ester that contact device is supplied with enters, with the operate continuously that be called in the phosphoric acid ester supply said process (A) that reclaimed carry out on one side.
By the smelly one-tenth component that has that carries out process (A) and operation (B) with periodical operation as described above or operate continuously, can lower containing in the phosphoric acid ester.
Make the number of occurrence of process (A) and process (B), with contain in the phosphoric acid ester have smelly one-tenth component, with rare gas element/or the contact conditions of water vapor etc. and different, can not determine entirely, but usually, preferably repeatedly to there being smelly one-tenth component to become below the desirable amount.Usually, with process (A) and process (B) the number of occurrence, preferably 1～10 time as a circulation time.
Below, the manufacture method of phosphoric acid ester of the present invention is described with reference to the accompanying drawings.Fig. 1 is the diagrammatic illustration figure of phosphoric acid ester manufacture method of the present invention.
Method shown in Figure 1 by utilizing the recycle system that mainly constitutes with receiver 1, fresh feed pump 2, heating part 3, packed tower 4 and cooling end 9, can lower the smelly one-tenth component that has that contains in the phosphoric acid ester.
At first, importing contains the phosphoric acid ester that smelly composition is arranged in receiver 1.
By fresh feed pump 2, in this receiver 1, phosphoric acid ester is imported heating part 3, with heating part 3 phosphoric acid ester is heated to specified temperature.
The phosphoric acid ester that is heated to specified temperature with heating part 3 is imported in the packed tower 4.In packed tower 4, phosphoric acid ester contacts with rare gas element and/or water vapor.In this occasion, phosphoric acid ester imports from the introducing port 5 that is provided in packed tower 4 tops, preferably utilizes gravity to fall downwards.On the other hand, rare gas element and/or water vapor preferably import from the gas introduction port 6 of the below that is provided in packed tower 4, discharge from the venting port 7 on the top that is provided in packed tower 4.Like this, under the situation in phosphoric acid ester and rare gas element and/or water vapor importing packed tower 4, improve both contact efficiencies.
Moreover, by with the contacting of rare gas element and/or water vapor, the smelly composition that has that contains in the phosphoric acid ester breaks away from from phosphoric acid ester, enters in rare gas element and/or the water vapor, discharges outside the system of packed tower 4 from venting port 7.
In addition,, discharge, be cooled to specified temperature with water cooler 9, while keep the mobile abundant inhibition pyrolysated state that becomes from the relief outlet 8 of packed tower 4 bottoms with rare gas element and/or the contacted phosphoric acid ester of water vapor.In the occasion of operate continuously, chilled phosphoric acid ester imports in the receiver 1 by valve 12, by stirring motor 13, utilizes agitating vane 14 to mix uniformly.
Be recovered in the phosphoric acid ester in the receiver 1, one side and the phosphoric acid ester that in receiver 1, has existed, in receiver 1, utilize agitating vane 14 to carry out sufficient blended simultaneously,, carry out and above-mentioned identical processing Yi Bian utilize fresh feed pump 2 to import in the packed tower 4 by stirring motor 13.In the occasion of periodical operation, chilled phosphoric acid ester is imported in the receiver 10.What contain in the phosphoric acid ester in being recovered to receiver 10 has smelly one-tenth component than desirable amount for a long time, after utilizing agitating vane 14 to mix uniformly, this phosphoric acid ester imports in the packed tower 4 by fresh feed pump 2 again, after cooling end 9 coolings, imports in the empty receiver 1.This operation proceeds to the smelly one-tenth component that has that contains in the phosphoric acid ester repeatedly and is reduced to desired amount.
Like this, there is smelly one-tenth component to be reduced to the phosphoric acid ester of desired amount, utilizes and open recovery valve 11, just can in receiver 1 or receiver 10, reclaim by fresh feed pump 2.
Add water in phosphoric acid ester, under reduced pressure distillate water, also can lower has smelly composition.
In phosphoric acid ester, add water, under reduced pressure will have smelly composition and water to distillate together, just can access the few phosphoric acid ester of foul smell.Utilize distillation to carry out distillating of water.
In phosphoric acid ester, add the method for water, except the method that before distillating water, adds entry, while also can be to distillate the method that water adds entry.Consider from this point of removal that smelly composition is arranged, while preferably distillate the method that water adds entry.The interpolation of water can be a successive, also can be intermittently, but successive suppresses moisture concentration easily, is best therefore.
Water that is added and the weight ratio of phosphoric acid ester (water/phosphoric acid ester) are good with 0.01～3.In this scope, there is the removal effect of smelly composition big, can lower the decomposition of phosphoric acid ester and painted.The weight ratio of above-mentioned water and phosphoric acid ester is more preferably 0.05～0.5, and preferably 0.1～0.3.Before adding water, contain the occasion of water in phosphoric acid ester, the content of its water comprises the amount of above-mentioned water.
Moreover in the present invention, the weight ratio of so-called above-mentioned water and phosphoric acid ester means the gross weight of water and the ratio of the gross weight of the phosphoric acid ester when (below, also be called during water distillates) during distillating water.
And then foaming in lowering the device of water distillating and gelation, the viewpoint that distillates water easily consider that the moisture concentration in the phosphoric acid ester during water distillates better is below the 10 weight %, is more preferably below the 5 weight %, preferably below the 3 weight %.In addition, handle the viewpoint consideration of lowering foul smell from utilizing water to distillate, the moisture concentration in the phosphoric acid ester during water distillates better is more than the 0.01 weight %, preferably more than the 0.1 weight %.Consider that from these viewpoints above-mentioned moisture concentration better is 0.01～10 weight %, is more preferably 0.1～5 weight %, preferably 0.1～3 weight %.
In addition, as mentioned above,, just distillating of water can be carried out, the decomposition of phosphoric acid ester can be suppressed in lower temperature owing under reduced pressure carry out distillating of water.In the present invention, if consider to have the vapour pressure of smelly composition, preferably below 30kPa, carry out distillating of water.Both reduced the temperature when distillating, and reduced the thermolysis of phosphoric acid ester again, for having removed smelly composition by distillating of water, such pressure better is below the 7kPa, preferably 1～4kPa.
Temperature when distillating water is considered from the viewpoint of the decomposition of removal that smelly composition is arranged and phosphoric acid ester, better is 60～150 ℃, preferably 80～120 ℃.
In addition, as the device that uses in the present invention, can enumerate the known device that in distillating method, uses.For example, as the batch distillation method, except steel basin, can be so that carry out with the general distiller that possesses film or heat exchanger etc. and the device of feed sump etc.In addition, in the occasion of using film or heat exchanger etc., can use general water distilling apparatus to carry out continuously.The batch distillation method, can lower more has smelly composition, thereby is best.
In addition, with above-mentioned phosphoric acid ester and rare gas element/or method that water vapor contacts in the same manner with after the phosphoric acid ester heating, can will in phosphoric acid ester, add water, under reduced pressure heat up in a steamer the process of anhydrating and the phosphoric acid ester refrigerative process that obtains in the said process is carried out repeatedly.
In addition, in that phosphoric acid agent and organic hydroxy compounds are reacted (below, be also referred to as phosphorylation reaction), when making phosphoric acid ester, can import rare gas element and react.
As the introduction method of rare gas element, different with the form of phosphorylation reaction, can not limit entirely.For example, in the occasion of batch distillation method, can enumerate the method that in gas phase part or liquid, imports rare gas element.Consider from more effectively lowering the viewpoint that smelly composition is arranged, preferably in liquid, import the method for rare gas element.By the using gas decollator, also can lower effectively has smelly composition.
Consider that from waste, the load that lowers vacuum apparatus that suppresses rare gas element, the viewpoint of avoiding high vacuum to necessitate the Intake Quantity of every 1kg organic hydroxy compounds and phosphoric acid agent, the import volume of rare gas element better are 0.0001～0.5m
3/ (hkg), 0.0001～0.05m preferably
3/ (hkg).Moreover, in the present invention, the " import volume (m of rare gas element
3/ (hkg) " flow when being standard state (0 ℃ of temperature, pressure 101.3kPa).
The importing of rare gas element, if in the phosphorylation reaction, just have no particular limits, but from the painted viewpoint consideration that suppresses to cause by inclusion of air, for example, before using the occasion of Vanadium Pentoxide in FLAKES, being preferably in the interpolation of Vanadium Pentoxide in FLAKES, promptly packing into of organic hydroxy compounds carries out after finishing as phosphoric acid agent.In addition, the importing of rare gas element can be carried out continuously, also can divide and carry out for several times.But from the painted viewpoint that suppresses to cause with remove the viewpoint consideration that smelly composition is arranged continuously, preferably carry out continuously by the oxidation of phosphoric acid ester.
In addition, from the viewpoint that prevents that elongated and productivity of reaction times from worsening, from the import volume that lowers rare gas element, the viewpoint of avoiding high vacuum to necessitate, and and then from the thermolysis of the phosphoric acid ester avoiding generating, prevent that the viewpoint of the deterioration of the increase that smelly composition is arranged that causes thus or color from considering, the temperature of reaction of organic hydroxy compounds and phosphoric acid agent better is 50～130 ℃, preferably 70～110 ℃.Reaction times is different with temperature of reaction, and can not determine entirely, but consider from the viewpoint that lowers remaining organic hydroxy compounds amount, better be about 5～20 hours, preferably about 8～15 hours.
Pressure during reaction has no particular limits, but viewpoint from the import volume that lowers rare gas element, and avoid reaction under the high temperature to necessitate and (avoid the thermolysis of phosphoric acid ester, prevent the increase that smelly composition is arranged that causes thus or the deterioration of color) viewpoint consider, better be under the following decompression of 70kPa, be more preferably under the following decompression of 20kPa, preferably under the decompression below the 10kPa.
As rare gas element, can enumerate nitrogen, argon gas, helium, carbonic acid gas etc.In these gases, preferentially select nitrogen and carbonic acid gas, override is selected nitrogen.
In addition, the phosphoric acid agent of Shi Yonging as mentioned above, is containing under the situation of water in the present invention, and the adjustment of reaction pressure is considered from the viewpoint of the deviation of the mol ratio of packing into that prevents to be caused by evaporation of water, preferably carries out from the state that does not have water in reactive system.For example, when temperature of reaction is 90 ℃, pack into finish after, the liquid temperature reaches as after 90 ℃ of the temperature of reaction of target, by adjusting reaction pressure, can prevent the deviation of the mol ratio of packing into that caused by evaporation of water.Moreover, because water vapor and phosphoric acid agent react in phosphorylation reaction, so the mol ratio of packing into produces deviation, and lower and prevent painted effect, thereby water vapor is unfavorable.Can use general moisture concentration determinator, for example Ka Er-Fei Xie coulometric titration device (flat natural pond industry (strain) system: AQUACOUNTERAQ-7) the intrasystem moisture concentration of assaying reaction.
In addition, in the phosphoric acid ester that obtains like this, there is pyrophosphorylation compound from phosphoric acid agent.Consider from the viewpoint of the increase that smelly composition is arranged that suppresses to result from this pyrophosphorylation compound, more wish to add water,, be preferably in 70～90 ℃ and be hydrolyzed at 50～100 ℃.
The phosphoric acid ester of the organic hydroxy compounds that obtains with such method, be that foul smell is few, can be directly or can be suitable as the surfactant composition of the base that uses in fields such as washing composition, emulsifying agent, fibre finish, rust-preventive agent and medical treatment product etc. as salt, more specifically be included in shampoo, washing composition, use in the agent of washing one's face etc.
With the increasing of phosphate ester salt concentration, viscosity is to increase intractable rapidly in the surfactant composition.But, can at least a kind the compound of selecting in the group of being made up of the polyvalent alcohol and the polyalkylene glycol of molecular weight below 5000 of carbonatoms 1～3 (a) will be contained, with the monohydroxy-alcohol (b) of carbonatoms 1～3, and the surfactant composition of the salt that the phosphoric acid ester (c) that smelly composition lowers is arranged that utilizes that method of the present invention obtains is as at 30 ℃ of temperature, velocity of shear 50s
-1The time viscosity be the following high concentration solution of 3000mPas.
In this occasion, the content that is (a) composition is that the content of 1～30 weight %, (b) composition is that the content of 1～8 weight %, (c) composition is the surfactant composition of 50～90 weight %.
As (a) composition, can enumerate the polyvalent alcohol of the carbonatoms 1～3 of ethylene glycol, propylene glycol etc., molecular weight below 50000, best polyether polyols such as the polyoxyethylene glycol of molecular weight below 3000, polypropylene glycol.Preferably dipropylene glycol, polypropylene glycol.These alcohol can use separately, do not mind even be used in combination also more than 2 kinds.
As (b) composition, can enumerate methyl alcohol, ethanol, propyl alcohol, preferably ethanol.
The salt of phosphoric acid ester can be by obtaining with alkaline matter neutralising phosphoric acid ester.As alkaline matter, can enumerate oxyhydroxide such as sodium hydroxide, potassium hydroxide, ammonium hydroxide, carbonate such as yellow soda ash, salt of wormwood, amines such as Monoethanolamine MEA BASF, diethanolamine, trolamine.Can use in these more than a kind.
The concentration of alkaline matter has no particular limits, and can at random set according to the effective constituent concentration of the phosphate ester salt of desirable organic hydroxy compounds, and also can use the solid state alkaline matter.Consider from the viewpoints such as easness of operation, preferably sodium hydroxide, potassium hydroxide.
The amount of alkaline matter (below, be called degree of neutralization), acid phosphoric acid ester better is 1.0～2.0 times of equivalent relatively, preferably 1.0～1.5 times of equivalent.Because reach 1.0 times more than the equivalent, the low-temperature stability of phosphate ester salt improves, because reach 2.0 times below the equivalent, does not show strong basicity, and operation becoming easily, and can avoid the corrosion of equipment etc.
Above-mentioned surfactant composition removes (a) composition, and (b) composition and (c) beyond the composition can also contain water, phosphoric acid, organic hydroxy compounds etc.Water can from the acid phosphoric acid ester and the time water, the water of interpolation etc. that generate.From the viscosity reduction of surfactant composition and the angle of raising point of ignition, preferably contain water in the surfactant composition.
In addition, in this surfactant composition, as required, can add other composition.As other composition, for example can enumerate antioxidants such as butyl hydroxy toluene, BHA, sanitass such as methyl p-hydroxybenzoate, discoloring agents such as hypochlorite (sodium, sylvite etc.), hydrogen peroxide, metal chelators such as ethylenediamine tetraacetic acid (EDTA), other pH buffer reagent etc.
Embodiment
Example I
Example I-1 (process A)
Undecyl alcohol (シ with 3 moles of ethylene oxide additions
エThe Le corporate system, trade(brand)name: ネ オ De-Le 1-3) 287.5g (0.95mol) and 85% phosphate aqueous solution 22.2g (quite Vanadium Pentoxide in FLAKES 0.096mol, water 0.474mol) mix, make temperature remain on 40～50 ℃ on one side, after adding 54.3g (0.377mol) Vanadium Pentoxide in FLAKES at leisure on one side, be warming up to 80 ℃, carry out reaction in 12 hours.After this, add the 18.2g ion exchanged water, carry out hydrolysis in 3 hours, obtain phosphoric acid ester at 80 ℃.(process B)
Then, make this phosphoric acid ester be warming up to 130 ℃ continuously on one side, on one side with 30g/min, from packed tower (internal diameter 50mm, high 22cm, the filler: Sumitomo heavy-duty machine tool industry (strain) system of pressure-controlling at 4kPa, trade(brand)name: cat head ス Le ザ-ラ ボ filler) is supplied with, at the bottom of tower, make the water vapor counter current contact with 90 ℃, 15g/min,, at the bottom of tower, obtain the phosphoric acid ester that smelly one-tenth component lowers through 3 minutes duration of contact.
Example I-2 (process A)
Undecyl alcohol that replacement is used in the process of example I-1 and 85% phosphate aqueous solution, use 262.5g (1.411mol) lauryl alcohol, 85% phosphoric acid 24.1g (being equivalent to Vanadium Pentoxide in FLAKES 0.105mol, water 0.514mol) and 77.4g (0.545mol) Vanadium Pentoxide in FLAKES, except not adding ion exchanged water, and the process A of example I-1 carries out phosphorylation reaction in the same manner, obtains phosphoric acid ester.(process B)
The phosphoric acid ester that will obtain in process A is warming up to 130 ℃ continuously on one side, on one side with 30g/min, from packed tower (internal diameter 50mm, high 55cm, the filler: Sumitomo heavy-duty machine tool industry (strain) system of pressure-controlling at 4kPa, trade(brand)name: cat head ス Le ザ-ラ ボ filler) is supplied with, at the bottom of tower, make the water vapor counter current contact with 90 ℃, 10g/min, through 8 minutes duration of contact, at the bottom of tower, obtain the phosphoric acid ester that smelly one-tenth component lowers.
Example I-3
In the process B of example I-1, except use irregular filler (external diameter 6mm, mesh 100 orders (Taylor's sieve mesh), the three special golden networking worker of association (strain) systems, trade(brand)name: MeMahon packing) in addition as filler, and example I-1 makes in the same manner, obtains the deodorization product.
Example I-4
Make in the packed tower that the phosphoric acid ester that obtains with the identical making of process A of example I-1 uses in the process B of example I-2, condition with 100 ℃ of temperature, pressure 1kPa, 8 minutes duration of contact and steam rates 21g/min, with the water vapor counter current contact, at the bottom of tower, obtain the phosphoric acid ester that smelly one-tenth component lowers.
Example I-5
In the process B of example I-1, except the pressure with packed tower is altered to 20kPa, and example I-1 makes in the same manner, obtains the phosphoric acid ester that smelly one-tenth component lowers.Comparative Example I-1
The process A of 200g and example I-1 is made the phosphoric acid ester (stink estimates 6) that the obtains equipment of packing in the same manner be blown in the intermittent type rapid steamer (four-hole boiling flask) of 500mL capacity of pipe, be warming up to 100 ℃ with pressure 2.7kPa.After this,, water vapor is blown into 3 hours to the intermittent type rapid steamer, obtains the phosphoric acid ester that smelly one-tenth component lowers with 90 ℃, the flow of 100g/h.Comparative Example I-2
In the process B of example I-1, except the temperature that contacts with phosphoric acid ester in the packed tower and water vapor is altered to 170 ℃ from 130 ℃, and example I-1 makes in the same manner, obtains the phosphoric acid ester that smelly one-tenth component lowers.Comparative Example I-3
In the process B of example I-1, except the temperature that contacts with phosphoric acid ester in the packed tower and water vapor is altered to 90 ℃ from 130 ℃, and example I-1 makes in the same manner, obtains the phosphoric acid ester that smelly one-tenth component lowers.Comparative Example I-4
In the process B of example I-1,, use rotating thin film formula rapid steamer (refreshing steel パ Application テ except replacing packed tower
StarNetwork (strain) system, model: 2-03 type, heat transfer area: 0.03m
2Glass), the feed speed that the feed speed of phosphoric acid ester is defined as 3g/min, water vapor is defined as 1.5g/min, duration of contact and is defined as the speed of rotation that 1 minute, pressure is defined as 4kPa, scraper plate and is defined as beyond the 400r/min, and example I-1 makes in the same manner, obtains the phosphoric acid ester that smelly one-tenth component lowers.
Then, according to following method the smelly phosphoric acid ester (phosphoric acid ester after the processing) that becomes component to lower of the phosphoric acid ester that obtains (phosphoric acid ester before handling) and having of obtaining is carried out stink evaluation and tone evaluation in the process A of each embodiment and each comparative example in process B.It the results are shown in the table 1.(stink evaluation)
In the glass wide-mouth specification bottle of capacity 110mL, put into before the processing of 50mL or the phosphoric acid ester after handling, 1 stink of directly smelling bottleneck of technician.The intensity of stink is divided into 0～6 (0 to serve as no stink, being that stink is strong with 6) 7 grades are according to its odor strength, by its evaluation of sensation decision.The 0th, no stink is the level that can use below 3.(tone evaluation)
Before will handling with ethanol or the phosphoric acid ester after handling be diluted to 10 weight %, put into the groove of silica glass system, with extinction photometer ((strain) Shimadzu Seisakusho Ltd. system, trade(brand)name: UV-1600), measure the absorbancy of wavelength 420nm, with its value as 1000 times.
Table 1
| The embodiment sequence number | ????I-1 | ????I-2 | ????I-3 | ????I-4 | ????I-5 | |
| Organic hydroxy compounds | Carbonatoms | ????11 | ????12 | ????11 | ????11 | ????11 |
| Oxyethane addition mole number | ????3 | ????0 | ????3 | ????3 | ????3 | |
| Contact conditions | Device | Packed tower (regular packing) | Packed tower (regular packing) | Packed tower (irregular filler) | Packed tower (regular packing) | Packed tower (regular packing) |
| The contact temperature [℃] | ????130 | ????130 | ????130 | ????100 | ????130 | |
| Pressure [kPa] | ????4 | ????4 | ????4 | ????1 | ????20 | |
| Rare gas element/phosphoric acid ester is than (m 3(standard state)/h)/(kg/h) | ????0.62 | ????0.37 | ????0.62 | ????0.87 | ????0.62 | |
| Duration of contact [min] | ????3 | ????8 | ????3 | ????8 | ????3 | |
| Processing speed [g/min] | ????30 | ????30 | ????30 | ????30 | ????30 | |
| Contact part volume [L] | ????0.43 | ????1.08 | ????0.43 | ????1.08 | ????0.43 | |
| Corresponding contact portion volumetrical processing speed [g/ (minL)] | ????69.5 | ????27.8 | ????69.5 | ????27.8 | ????69.5 | |
| Stink is estimated | Before the processing | ????6 | ????6 | ????6 | ????6 | ????6 |
| After the processing | ????2 | ????2 | ????2 | ????3 | ????4 | |
| Tone is estimated | Before the processing | ????4 | ????4 | ????4 | ????4 | ????4 |
| After the processing | ????4 | ????5 | ????4 | ????4 | ????4 | |
Table 1 (continuing)
| The comparative example sequence number | ????I-1 | ????I-2 | ????I-3 | ????I-4 | |
| Organic hydroxy compounds | Carbonatoms | ????11 | ????11 | ????11 | ????11 |
| Oxyethane addition mole number | ????3 | ????3 | ????3 | ????3 | |
| Contact conditions | Device | The intermittent type rapid steamer | Packed tower (regular packing) | Packed tower (regular packing) | Rotating thin film formula rapid steamer |
| The contact temperature [℃] | ????100 | ????170 | ????90 | ????130 | |
| Pressure [kPa] | ????2.7 | ????4 | ????4 | ????4 | |
| Rare gas element/phosphoric acid ester is than (m 3(standard state)/h)/(kg/h) | ????1.86 | ????0.62 | ????0.62 | ????0.62 | |
| Duration of contact [min] | ????180 | ????3 | ????3 | ????1 | |
| Processing speed [g/min] | ????2.2 | ????30 | ????30 | ????3 | |
| Contact part volume [L] | ????0.5 | ????0.43 | ????0.43 | ????0.47 | |
| Corresponding contact portion volumetrical processing speed [g/ (minL)] | ????4.4 | ????69.5 | ????69.5 | ????6.3 | |
| Stink is estimated | Before the processing | ????6 | ????6 | ????6 | ????6 |
| After the processing | ????4 | ????6 | ????5 | ????3 | |
| Tone is estimated | Before the processing | ????4 | ????4 | ????4 | ????4 |
| After the processing | ????10 | ????300 | ????4 | ????4 | |
From the result shown in the table 1 as can be known, according to each embodiment, can access stink with big processing speed and lower and the good phosphoric acid ester of tone.
On the other hand, from Comparative Example I-1 and I-4 as can be known, because use intermittent type or rotating thin film formula rapid steamer, so processing speed is little.In addition, from Comparative Example I-2 as can be known, contact temperature height, therefore
Stink evaluation and tone are estimated deterioration significantly.From Comparative Example I-3 as can be known, the contact temperature is low, so the stink evaluation does not almost improve.
In addition, according to the manufacture method of each embodiment, compare with the intermittent type of degree size or the situation of rotating thin film formula rapid steamer with use, lowering with higher processing speed has smelly one-tenth component, can obtain stink evaluation and tone easily and estimate good phosphoric acid ester.
And then, according to the manufacture method of each embodiment, be identical occasion in processing speed, use the more small-sized packed tower of rotating thin film formula rapid steamer than in the past, efficient be can make easily and stink, phosphoric acid ester that tone is good lowered well.
Example II
Example II-1 (manufacturing of phosphoric acid ester)
Undecyl alcohol (シ with 3 moles of ethylene oxide additions
エThe Le corporate system, trade(brand)name: ネ オ De-Le 1-3) 862.5g (2.85mol) and 85% phosphate aqueous solution 66.6g (quite Vanadium Pentoxide in FLAKES 0.288mol, water 1.422mol) mix, make temperature remain on 40～50 ℃ on one side, after adding 162.9g (1.13mol) Vanadium Pentoxide in FLAKES at leisure on one side, be warming up to 80 ℃, carry out reaction in 12 hours.After this, in this reaction mixture, add the 54.6g ion exchanged water, carry out hydrolysis in 3 hours, obtain phosphoric acid ester at 80 ℃.
Investigate the stink evaluation (the stink evaluation of the phosphoric acid ester at initial stage) of resulting phosphoric acid ester in the same manner with example I.It the results are shown in the table 2.(process A (the 1st time))
As shown in Figure 1, use with pipe arrangement connection 2L volumetrical receiver 1 and receiver 10 and packed tower (internal diameter 50mm, high 22cm, filler: Sumitomo heavy-duty machine tool industry (strain) system, trade(brand)name: ス Le ザ-ラ ボ filler: device Unit 4).
In receiver 1, import the above-mentioned phosphoric acid ester that obtains of 500g.On one side will be warming up to 130 ℃ continuously with heating part 3 by the phosphoric acid ester that fresh feed pump 2 imports from the bottom of this receiver 1, on one side become in the packed tower 4 of 4kPa to supply with the pressure-controlling of flow 25g/min in cat head, meanwhile at the bottom of the tower of packed tower 4, supply with water vapor with flow 5g/min, make thus phosphoric acid ester and water vapor with 130 ℃, 1 by be duration of contact carried out counter current contact in 3 minutes after, the relief outlet 8 at the bottom of tower is discharged phosphoric acid ester.1 by being duration of contact the phosphoric acid ester supplied with from the introducing port 5 at the top of packed tower 4 until when the relief outlet 8 of packed tower 4 bottoms is discharged, the time that contacts with water vapor in the inside of packed tower 4.(process B)
The phosphoric acid ester of the 1st time of process A discharging is cooled to 60 ℃ continuously with cooling end 9, returns receiver 1 then.(process A (after the 2nd time))
The phosphoric acid ester returned and the phosphoric acid ester in the receiver 1 are mixed, on one side and above-mentioned in the same manner from the bottom of receiver 1 by fresh feed pump 2 to packed tower 4 supplies, make phosphoric acid ester and water vapor with 130 ℃, 1 by being duration of contact to carry out counter current contact in 3 minutes.
Carry out after the 2nd time of process A repeatedly and process B, the reciprocal time when the 1st time of process A begins is defined as 40 minutes.
The average contact time of the duration of contact of the initial stage phosphoric acid ester full dose of the receiver 1 among the process A is 6 minutes relatively.In addition, after process A is finished, carry out cooling operation, therefore be 6 minutes identical with average contact time the average heat-up time in the time of 130 ℃.Average contact time is according to formula (I):
(average contact time)=(recycle to extinction amount) ÷ (initial stage phosphoric acid ester amount) *
(1 is passed through duration of contact) (I) obtained.
In the present embodiment, carry out circulation in 40 minutes with 25g/min, so the recycle to extinction amount is 1000g, initial stage phosphoric acid ester amount is 500g.
Reclaim phosphoric acid ester and above-mentioned its stink of investigating in the same manner of having smelly composition to lower of obtaining like this from recovery valve 11 and estimate (the stink evaluation of the phosphoric acid ester after the processing).It the results are shown in the table 2.
Example II-2
In the process B of example II-1, do not make the phosphoric acid ester of discharging among the process A return receiver 1, but switching valve 12, after returning receiver 10, by the bottom of fresh feed pump 2, again after packed tower 4 is supplied with the phosphoric acid ester of returning from receiver 10, be transformed into and be called the periodical operation of returning receiver 1, in addition, and example II-1 makes in the same manner, obtains phosphoric acid ester.
Investigate the resulting phosphoric acid ester stink evaluation that has smelly composition to lower in the same manner with example I.It the results are shown in the table 2.
Example II-3 (manufacturing of phosphoric acid ester)
Replace 862.5g (2.85mol) undecyl alcohol and 85% phosphate aqueous solution 66.6g and 162.9g (1.13mol) Vanadium Pentoxide in FLAKES in the example II-1, use 840.0g (4.516mol) lauryl alcohol, 85% phosphoric acid 77.2g (being equivalent to Vanadium Pentoxide in FLAKES 0.336mol, water 1.644mol) and 251.4g (1.744mol) Vanadium Pentoxide in FLAKES, and do not add ion exchanged water, in addition, and example II-1 makes in the same manner, obtains phosphoric acid ester.
Investigate the resulting phosphoric acid ester stink evaluation that has smelly composition to lower in the same manner with example I.It the results are shown in the table 2.(process A and process B)
Use the above-mentioned phosphoric acid ester that obtains, in the process A of example II-1, by with 1 by being altered to 6 minutes from 3 minutes duration of contact, make average contact time and average heat-up time be altered to 12 minutes respectively, in addition cooling temperature is altered to 80 ℃ from 60 ℃, in addition, and example II-1 makes in the same manner, obtains phosphoric acid ester.
Investigate the resulting phosphoric acid ester stink evaluation that has smelly composition to lower in the same manner with example I.It the results are shown in the table 2.
Example II-4
In the process A of example II-1, as the filler that is filled in the packed tower 4, use irregular filler (the three special golden networking worker of association (strain) systems, trade(brand)name: MeMahon packing, external diameter 6mm, mesh 100 orders (Taylor's sieve mesh)), in addition, and example II-1 makes in the same manner, obtains phosphoric acid ester.
Investigate the resulting phosphoric acid ester stink evaluation that has smelly composition to lower in the same manner with example I.It the results are shown in the table 2.
Example II-5
In the process A of example II-1, replace packed tower 4, use rotating thin film formula rapid steamer (refreshing steel パ Application テ
ッNetwork (strain) system, model: 2-03 type, heat transfer area: 0.03m
2, glass), in process A, by with phosphoric acid ester and water vapor 1 by being altered to 2 minutes duration of contact, make average contact time and average heat-up time be altered to 4 minutes respectively, in addition, and example II-1 makes in the same manner, obtains phosphoric acid ester.
Investigate the resulting phosphoric acid ester stink evaluation that has smelly composition to lower in the same manner with example I.It the results are shown in the table 2.
Example II-6
In the process A of example II-1, replace packed tower 4, use intermittent type contact device (glass, 2L volumetrical four-hole boiling flask, equipment is blown into pipe), make the phosphoric acid ester amount that imports in the receiver 1 reach 1000g, 100 ℃ of contact temperature, pressure 2kPa, supply with water vapor with flow 12.5g/min, make the value of the throughput ratio of rare gas element/phosphoric acid ester reach 0.5 thus, by 1 during will infeeding that phosphoric acid ester in the intermittent type contact device discharges by being altered to 30 minutes duration of contact, the reciprocal time of process A and process B is altered to 120 minutes, make average contact time and average heat-up time be altered to 90 minutes respectively, in addition, and example II-1 makes in the same manner, reaches phosphoric acid ester.
Investigate the resulting phosphoric acid ester stink evaluation that has smelly composition to lower in the same manner with example I.It the results are shown in the table 2.Comparative Example I I-1
In the process B of example II-1, except making phosphoric acid ester be cooled to 60 ℃, and maintain beyond 130 ℃, and example II-1 makes in the same manner without cooling end 9, obtain phosphoric acid ester.In process B, the temperature of phosphoric acid ester also is 130 ℃, and therefore average heat-up time is identical with reciprocal time to be 40 minutes.
Investigate the resulting phosphoric acid ester stink evaluation that has smelly composition to lower in the same manner with example I.It the results are shown in the table 2.Comparative Example I I-2
In the process B of example II-6, except making phosphoric acid ester be cooled to 60 ℃, and make its temperature maintenance beyond 100 ℃, and example II-6 make in the same manner without cooling end 9, obtain phosphoric acid ester.In process B, the temperature of phosphoric acid ester also is 100 ℃, and therefore average heat-up time is identical with reciprocal time to be 120 minutes.
Investigate the resulting phosphoric acid ester stink evaluation that has smelly composition to lower in the same manner with example I.It the results are shown in the table 2.
Table 2
| The embodiment sequence number | ????II-1 | ????II-2 | ????II-3 | ????II-4 | ????II-5 | ????II-6 | ||
| Organic hydroxy compounds | Carbonatoms | ????11 | ????11 | ????12 | ????11 | ????11 | ????11 | |
| Oxyethane addition mole number | ????3 | ????3 | ????0 | ????3 | ????3 | ????3 | ||
| Contact conditions | Device | Packed tower (regular packing) | Packed tower (regular packing) | Packed tower (regular packing) | Packed tower (irregular filler) | Stir the membranous type rapid steamer | The intermittent type contact device | |
| The contact temperature (℃) | ????130 | ????130 | ????130 | ????130 | ????130 | ????100 | ||
| Pressure (kPa) | ????4 | ????4 | ????4 | ????4 | ????4 | ????2 | ||
| The throughput ratio [(m of rare gas element/phosphoric acid ester 3/h)/(kg/h)] | ????0.25 | ????0.25 | ????0.25 | ????0.25 | ????0.25 | ????0.5 | ||
| Average contact time (min) | ????6 | ????6 | ????12 | ????6 | ????4 | ????90 | ||
| Average heat-up time (min) | ????6 | ????6 | ????12 | ????6 | ????4 | ????90 | ||
| Operation | Continuously | Intermittently | Continuously | Continuously | Continuously | Continuously | ||
| Cooling conditions: cooling temperature (℃) | ????60 | ????60 | ????80 | ????60 | ????60 | ????60 | ||
| Stink is estimated | Initial stage | ????6 | ????6 | ????6 | ????6 | ????6 | ????6 | |
| After the processing | ????2 | ????2 | ????2 | ????2 | ????2 | ????3 | ||
Table 2 (continuing)
| The comparative example sequence number | ????II-1 | ????II-2 | |
| Organic hydroxy compounds | Carbonatoms | ????11 | ????11 |
| Oxyethane addition mole number | ????3 | ????3 | |
| Contact conditions | Device | Packed tower (regular packing) | The intermittent type contact device |
| The contact temperature (℃) | ????130 | ????100 | |
| Pressure (kPa) | ????4 | ????2 | |
| The throughput ratio [(m of rare gas element/phosphoric acid ester 3/h)/(kg/h)] | ????0.25 | ????0.5 | |
| Average contact time (min) | ????6 | ????90 | |
| Average heat-up time (min) | ????40 | ????120 | |
| Operation | Continuously | Continuously | |
| Cooling conditions: cooling temperature (℃) | Do not have | Do not have | |
| Stink is estimated | Initial stage | ????6 | ????6 |
| After the processing | ????5 | ????5 | |
From the result shown in the table 2 as can be known,, behind the heated phosphoric ester, rare gas element is contacted with this phosphoric acid ester, then repeat to be called and make the operation of this phosphoric acid ester refrigerative, so efficient is removed the smelly composition that has that contains in the phosphoric acid ester well according to each embodiment.
EXAMPLE IIIProduction Example III-1
The former phosphoric acid 75.0g that mixes 819.8g (4.40mol) lauryl alcohol and 85% weight % in 2000mL volumetrical reaction vessel is (if as P
2O
5NH
2O represents, P
2O
546.2g (0.32mol) H
2O28.8g (1.60mol)), Yi Bian make temperature remain on 60～70 ℃,, carry out reaction in 12 hours Yi Bian after adding 247.4g (1.74mol) Vanadium Pentoxide in FLAKES (effective constituent 98.5 weight %) at leisure, be warming up to 80 ℃.The value of formula (1) is 2.9.The stink evaluation of resulting phosphoric acid ester is 5, and stink is strong, can not be to cooperations such as washing composition.
EXAMPLE III-1
The phosphoric acid ester that obtains with Production Example III-1 is moved on in the water distilling apparatus of intermittent type steel basin of the 500mL that can add water continuously, after being decompressed to 2.7kPa, be warming up to 90 ℃ on one side, on one side with the speed of 20g/h, in phosphoric acid ester, add water continuously with 2 hours, distill (Total Water 40g).The moisture concentration that measure in the phosphoric acid ester this moment is 0.2～1.0 weight %.
The phosphoric acid ester that obtains by this operation and above-mentioned be 2 when carrying out in the same manner that stink is estimated, stink is few.
Use Ka Er-Fei Xie coulometric titration device (flat natural pond industry (strain) system, trade(brand)name: the moisture concentration in mensuration phosphoric acid ester AQUACOUNTER AQ-7).Comparative Example I II-1
In the distillation of the phosphoric acid ester 250g that obtains with Production Example III-1 that in the device identical, packs into, do not add water, in addition, carry out and EXAMPLE III-1 identical operations with EXAMPLE III-1.Do not detect the moisture in the distillation.The stink evaluation of resulting phosphoric acid ester is 5, does not almost change before the strong and distillation of stink, can not cooperate to washing composition etc.Comparative Example I II-2
The phosphoric acid ester 250g that the reaction with Production Example III-1 of packing in the device identical with EXAMPLE III-1 obtains is blown into the water vapor except the interpolation with water becomes, and carries out with the condition identical with EXAMPLE III-1.After being decompressed to 2.7kPa, be warming up to 90 ℃, stir on one side, on one side with the speed of 20g/h, in phosphoric acid ester, add water vapor continuously with 2 hours, distill (Total Water 40g).The moisture concentration that measure in the phosphoric acid ester this moment is 0.3～1.1 weight %.The stink evaluation of resulting phosphoric acid ester is 4, improve a little, but stink is strong, can not be to cooperations such as washing composition.
For the functional evaluation that makes the above-mentioned phosphoric acid ester that obtains reaches is the level " 3 " that possible use, must be blown into 10 hours water vapors with above-mentioned condition again, carries out deodorization.Production Example III-2
Can react with distillatory and have in the 1000mL volumetrical device of the stirrer that can add water continuously, mix the undecyl alcohol (シ of 3 moles of ethylene oxide additions
ェThe Le corporate system, trade(brand)name: ネ オ De-Le 1-3) 287.5g (0.95mol), 85% phosphoric acid 22.2g are (if as P
2O
5NH
2O represents, P
2O
513.7g (0.096mol), H
2O8.5g (0.474mol)), Yi Bian be that temperature remains on 40～50 ℃,, carry out reaction in 12 hours Yi Bian after adding 54.3g (0.38mol) Vanadium Pentoxide in FLAKES (effective constituent 98.5 weight %) at leisure, be warming up to 80 ℃.The value of formula (1) is 3.0.The stink evaluation of resulting phosphoric acid ester is 6, and stink is strong, can not be to cooperations such as washing composition.After this, add 15g water (moisture concentration in the phosphoric acid ester becomes 4.0 weight %), 80 ℃, carry out hydrolysis in 2 hours at normal pressure.
EXAMPLE III-2
After being decompressed to 2.0kPa,,, distill (Total Water 125g) Yi Bian in phosphoric acid ester, add water continuously with the speed of 25g/h, with 5 hours Yi Bian make the phosphoric acid ester full dose that obtains with Production Example III-2 be warming up to 80 ℃.At this moment, the moisture concentration of measuring in the phosphoric acid ester is 0.8～2.7.
The stink evaluation of the phosphoric acid ester that is obtained by this operation is 3, and stink is few.Production Example III-3
Use pump from the reaction vessel of 2000mL to the vaporizer liquor charging that flows down film type, carry out underpressure distillation after, use the device that in former reaction vessel, possesses retrieval system to carry out.At first, in reaction vessel, mix the former phosphatase 11 17.2g of 931.5g (5.00mol) lauryl alcohol and 85% weight (if as P
2O
5NH
2O represents, P
2O
5(72.4g (0.51mol) H
2O45.1g (2.50mol)), Yi Bian make temperature remain on 60～70 ℃,, carry out reaction in 12 hours Yi Bian after adding 292.4g (2.03mol) Vanadium Pentoxide in FLAKES (effective constituent 98.5 weight %) at leisure, be warming up to 80 ℃.The value of formula (1) is 2.95.The stink evaluation of resulting phosphoric acid ester is 5, and stink is strong, can not be to cooperations such as washing composition.
EXAMPLE III-3
On one side add water continuously with the speed of 53g/h in reaction vessel, be decompressed to 2.7kPa in the device Yi Bian make, use pump, the phosphoric acid ester that Production Example III-3 obtained with 30kg/h are distilled to the vaporizer liquor charging that flows down film type.At this moment, on one side the temperature in the reaction vessel is controlled at 50～60 ℃, the temperature that thin-film evaporator is exported is controlled at 100 ℃, carries out distillation (Total Water 265g) in 5 hours on one side.The moisture concentration of measuring in the phosphoric acid ester in reaction vessel this moment is 1.0～2.0 weight %.
The stink evaluation of the phosphoric acid ester that is obtained by this operation is 2, and stink is few.
EXAMPLE IV
EXAMPLE IV-1
Ethoxylate (trade(brand)name ネ オ De-Le 1-3, シ with the higher alcohols of carbonatoms 11, branching rate 20%, average oxyethane (EO) addition mole number 3
ェThe Le corporate system, molecular weight 298.6) 548g (1.84mol) and 85% phosphatase 24 3g (being equivalent to Vanadium Pentoxide in FLAKES 0.19mol, water 0.92mol) mixing.Then, with 1300mL/min (0.11m
3/ (hrkg): standard state) import nitrogen, add 109g (0.76mol) Vanadium Pentoxide in FLAKES at leisure 40～70 ℃ of temperature to gas phase portion.After being warming up to 90 ℃, in reactive system, do not have water after, pressure 101.3kPa carry out 8 hours the reaction.After this, add ion exchanged water 14.0g, carry out hydrolysis in 3 hours at 90 ℃.
EXAMPLE IV-2
Ethoxylate (trade(brand)name ネ オ De-Le 1-3, シ with the higher alcohols of carbonatoms 11, branching rate 20%, average oxyethane (EO) addition mole number 3
ェThe Le corporate system, molecular weight 298.6) 548g (1.84mol) and 85% phosphatase 24 3g (being equivalent to Vanadium Pentoxide in FLAKES 0.19mol, water 0.92mol) mixing.Then, with 140mL/min (0.012m
3/ (hrkg): standard state) in liquid, import nitrogen, add Vanadium Pentoxide in FLAKES 109g (0.76mol) at leisure 40～70 ℃ of temperature.After being warming up to 90 ℃, in reactive system, do not have water after, be decompressed to 2.67kPa carry out 8 hours the reaction.After this, under normal pressure, add ion exchanged water, carry out hydrolysis in 3 hours at 90 ℃.
EXAMPLE IV-3
Pressure when carrying out phosphorylation except making reaches the 50kPa, and EXAMPLE IV-1 is carried out phosphorylation reaction in the same manner.
EXAMPLE IV-4
Except the nitrogen amount that makes importing reaches 3000mL/min (0.26m
3/ (hrkg): standard state) in addition, and EXAMPLE IV-1 is carried out phosphorylation reaction in the same manner.Comparative Example I V-1
Behind the ethoxylate and the mixing of 85% phosphoric acid with higher alcohols, except not importing nitrogen, and EXAMPLE IV-1 is carried out phosphorylation reaction in the same manner.Comparative Example I V-2
Except not importing nitrogen, and EXAMPLE IV-3 is carried out phosphorylation reaction in the same manner.(mensuration of phosphoric acid one ester, phosphodiester and former phosphoric acid amount)
Accurately weighing 1g test portion adds 100mL ethanol, 50mL water, dissolves.Use the 1/2N potassium hydroxide aqueous solution to carry out the potential difference titration, measure the 1st stoichiometric point (AV1) and the 2nd stoichiometric point (AV2).
Then, accurately weighing 1g test portion carries out in the dissolved sample at adding 100mL ethanol, 50mL water, adds the about 20mL of 2N calcium chloride water, uses the 1/2N potassium hydroxide aqueous solution, carries out the potential difference titration, measures the 3rd stoichiometric point (AV3).Calculate the amount of phosphoric acid one ester, phosphodiester and former phosphoric acid according to formula (2)～(4).
Former phosphoric acid amount (weight %)=(AV3-AV2) * 98/56108 (2)
Phosphodiester (weight %)
=(2AV1-AV2) * phosphodiester molecular weight/56108 (3)
Phosphoric acid one ester (weight %)
=(2AV2-AV1-AV3) * phosphoric acid one ester molecule amount/56108 (4) (mensuration of sherwood oil soluble part)
Accurate weighing 5g test portion, Yi Bian add sherwood oil, ethanol and trolamine 15 each 100mL of the volume % aqueous solution, Yi Bian in the separating funnel of 500mL, carry out layering (A).Utilize other 500mL volumetrical separating funnel, add the 100mL sherwood oil, make this lower floor's layering (B).(A) make this lower floor's layering (C) in the same manner.Each upper strata of mixing (A), (B), (C) after the aqueous solution of usefulness ethanol 50% volume is cleaned 2 times, makes the sherwood oil evaporation, the sherwood oil soluble part that obtains extracting in 60 ℃ hot water bath.Calculate the amount of sherwood oil soluble part according to formula (5).So-called sherwood oil soluble part is a unreacted organic hydroxy compounds or from the compound of organic hydroxy compounds, is to contain the compound that smelly composition is arranged.
(mensuration of the amount of sherwood oil soluble part)=
(weight (g) of the sherwood oil soluble part that extracts/
(test portion weight (g) * 100 (5) (tone)
Measure in the same manner with example I.(stink evaluation)
Neutralize with 48% potassium hydroxide aqueous solution, so that test portion forms effective constituent 27% (being phosphoric acid one ester+phosphodiester, the phosphoric acid ester benchmark).
This phosphate ester salt of 50mL is sampled in the 110mL volumetrical glass wide-mouth specification bottle, and 1 skilled technician directly smells the stink of bottleneck, estimates with 7 grades of 0 (odorless)～6 (by force).
Table 3
(notes) mol ratio
1}: ethoxylate/H
2O/P
2O
5
| Embodiment | Comparative example | ||||||
| ????IV-1 | ???IV-2 | ???IV-3 | ????IV-4 | ????IV-1 | ???IV-2 | ||
| Condition | Mol ratio 1} | ????1.94/0.97/1.0 | |||||
| Temperature (℃) | ????90 | ||||||
| Time (hr) | ????8 | ||||||
| Pressure (kPa) | ????101.3 | ????2.67 | ????50 | ????101.3 | ????101.3 | ????50 | |
| Nitrogen flow (mL/min) (m 3/hr·kg) | ????1,300 ????0.11 | ????140 ????0.012 | ????1,300 ????0.11 | ????3,000 ????0.26 | Do not have | Do not have | |
| Estimate | Phosphoric acid one ester (weight %) | ????73.1 | ????73.3 | ????73.3 | ????73.0 | ????72.7 | ????72.6 |
| Phosphodiester (weight %) | ????20.4 | ????21.2 | ????21.0 | ????20.0 | ????19.9 | ????20.0 | |
| Former phosphoric acid (weight %) | ????4.1 | ????3.8 | ????3.9 | ????4.0 | ????4.2 | ????4.2 | |
| Sherwood oil soluble part (weight %) | ????1.5 | ????1.2 | ????1.2 | ????1.5 | ????2.0 | ????1.9 | |
| Tone is estimated | ????3 | ????3 | ????3 | ????3 | ????115 | ????110 | |
| Stink is estimated | ????4 | ????3 | ????3.5 | ????3.5 | ????6 | ????6 | |
From the result shown in the table 3 as can be known, the phosphoric acid ester that obtains in EXAMPLE IV-1～IV-4 is all than the excellent color tone of the phosphoric acid ester that obtains in Comparative Example I V-1 and Comparative Example I V-2, and stink is few.
EXAMPLE VProduction Example V-1
Undecyl alcohol (the シ that mixes 3 moles of ethylene oxide additions
ェThe Le corporate system, trade(brand)name ネ オ De-Le 1-3) 862.5g (2.854mol), 85% phosphoric acid 66.6g (being equivalent to Vanadium Pentoxide in FLAKES 0.288mol, water 1.422mol), make temperature remain on 40～50 ℃ on one side, after adding 162.9g (1.13mol) at leisure on one side, be warming up to 80 ℃, carry out reaction in 12 hours.The value of formula (1) is 3.0.After this, add the 54.6g ion exchanged water, carry out hydrolysis in 3 hours at 80 ℃.The moisture concentration of resulting phosphoric acid ester is 4.8 weight %, carries out the result that stink is estimated, and foul smell is strong, and evaluation is 6, can not be to uses such as washing composition.
EXAMPLE V-1
Use periodical operation, at 80 ℃, the phosphoric acid ester 300g that 3kPa, decompression in 3 hours will obtain in Production Example V-1 down dewaters.Its result, moisture concentration becomes 1.2 weight %.Make the phosphoric acid ester that obtains be warming up to 130 ℃ continuously on one side, on one side with 30g/min, from packed tower (internal diameter 50mm, high 22cm, the filler: Sumitomo heavy-duty machine tool industry (strain) system of pressure-controlling at 4kPa, trade(brand)name: cat head ス Le-ザ-ラ ボ filler) is supplied with, make at the bottom of the tower water vapor carry out counter current contact with 90 ℃, 15g/min, through 3 minutes duration of contact, at the bottom of tower, obtain the deodorization product.In this operation, almost can't see foaming, can handle operation no problemly.The gained phosphoric acid ester, stink is evaluated as 2, and is good.
In the 258.8g phosphoric acid ester that obtains like this, add 7.0g ethanol, 21.0g dipropylene glycol, after forming uniform solution, add 48% potassium hydroxide aqueous solution 60.6g and ion exchanged water 3.0g, stir, obtain the aqueous solution of transparent and uniform high concentration phosphorus acid esters salt.The resulting aqueous solution, phosphate ester salt are 67.9 weight %, and ethanol is 2.0 weight %, and dipropylene glycol is 6.0 weight %, viscosity (30 ℃, velocity of shear 50s
-1) be 870mPas.Production Example V-2
The undecyl alcohol that replaces the 3 moles of ethylene oxide additions of Production Example V-1, use 968.3g (4.516mol) tetradecyl alcohol, with 85% phosphoric acid 77.2g (being equivalent to Vanadium Pentoxide in FLAKES 0.336mol, water 1.644mol) and 251.4g (1.744mol) Vanadium Pentoxide in FLAKES, react, in addition, V-1 makes in the same manner with Production Example, obtains phosphoric acid ester.The value of formula (1) is 3.0.After this, add the 25.9g ion exchanged water, carry out hydrolysis in 3 hours at 80 ℃.The moisture concentration of resulting phosphoric acid ester is 1.8 weight %, is 5 according to the stink evaluation of stink evaluation, can not be to uses such as washing composition.
EXAMPLE V-2
Use the device identical to carry out with EXAMPLE V-1.Make the part of the phosphoric acid ester that in Production Example V-2, obtains be warming up to 130 ℃ continuously on one side, on one side with 30g/min, from packed tower (internal diameter 50mm, high 22cm, the filler: Sumitomo heavy-duty machine tool industry (strain) system of pressure-controlling at 4kPa, trade(brand)name: cat head ス Le-ザ-ラ ボ filler) is supplied with, convert by standard state (0 ℃, 101.3kPa), flow with 200mL/min, at the bottom of tower, make nitrogen and phosphoric acid ester carry out counter current contact, through 3 minutes duration of contact, at the bottom of tower, obtain the deodorization product.In this operation, also can't see foaming, can handle operation no problemly.The stink evaluation of resulting phosphoric acid ester is 2.5, is good.
Brief description of drawings
Fig. 1 is the diagrammatic illustration figure of phosphoric acid ester manufacture method of the present invention.The explanation of symbol
1 receiver
2 fresh feed pumps
3 heating parts
4 packed towers
5 introducing ports
6 gas introduction ports
7 venting ports
8 relief outlets
9 cooling ends
10 receivers
11 recovery valves
12 valves
13 stirring motors
14 agitating vanes
Claims (14)
1. the manufacture method of phosphoric acid ester, this manufacture method is that 100～160 ℃ phosphoric acid ester is contacted with rare gas element and/or water vapor.
2. manufacture method according to claim 1 wherein, makes phosphoric acid ester and rare gas element contact with/water vapor under the pressure below the 20kPa.
3. manufacture method according to claim 1 and 2 wherein, makes phosphoric acid ester contact with water vapor.
4. the manufacture method of phosphoric acid ester, this manufacture method is with behind (A) heated phosphoric ester, makes process that this phosphoric acid ester contacts with rare gas element and/or water vapor and (B) the phosphoric acid ester refrigerative process that obtains in process (A) is carried out repeatedly.
5. manufacture method according to claim 4, wherein, in process (A), the temperature when the heated phosphoric ester makes phosphoric acid ester contact with rare gas element and/or water vapor is adjusted to 100～160 ℃, in process (B), the cooling temperature of phosphoric acid ester is adjusted to below 90 ℃.
6. according to claim 4 or 5 described manufacture method, wherein, phosphoric acid ester is contacted with rare gas element and/or water vapor.
7. according to each the described manufacture method in the claim 4～6, wherein, phosphoric acid ester is contacted with water vapor.
8. according to each the described manufacture method in the claim 4～7, wherein, the moisture content in phosphoric acid ester be the state below the 3 weight % make phosphoric acid ester and rare gas element/or water vapor contact.
9. the manufacture method of phosphoric acid ester, this manufacture method is to add entry in phosphoric acid ester, under reduced pressure heats up in a steamer and anhydrates.
10. manufacture method according to claim 9, wherein, the moisture content in the phosphoric acid ester during water distillates is below the 10 weight %.
11., wherein, behind (C) heated phosphoric ester, in phosphoric acid ester, add entry, under reduced pressure heat up in a steamer the process of anhydrating, and (D) make the phosphoric acid ester refrigerative process that in process (C), obtains repeatedly according to claim 9 or 10 described manufacture method.
12. the manufacture method of phosphoric acid ester, this manufacture method are when making the reaction of organic hydroxy compounds and phosphoric acid agent make phosphoric acid ester, import rare gas element and react.
13. manufacture method according to claim 12 wherein, is reacted under the decompression below the 70kPa.
14. according to claim 12 or 13 described manufacture method, wherein, rare gas element is a nitrogen.
Applications Claiming Priority (10)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2001165400A JP3873664B2 (en) | 2001-05-31 | 2001-05-31 | Vehicle frame structure |
| JP165040/01 | 2001-05-31 | ||
| JP165056/01 | 2001-05-31 | ||
| JP2001165560A JP3737037B2 (en) | 2001-05-31 | 2001-05-31 | Printing device |
| JP2001291848A JP4497503B2 (en) | 2001-09-25 | 2001-09-25 | Production method of phosphate ester |
| JP291848/01 | 2001-09-25 | ||
| JP355203/01 | 2001-11-20 | ||
| JP2001355203A JP3596768B2 (en) | 2001-11-20 | 2001-11-20 | Method for producing phosphate ester |
| JP355728/01 | 2001-11-21 | ||
| JP2001355728A JP3617830B2 (en) | 2001-11-21 | 2001-11-21 | Production method of phosphate ester |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100046769A Division CN1315853C (en) | 2001-05-31 | 2002-05-30 | Process for preparing phosphoric ester |
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| CN1389467A true CN1389467A (en) | 2003-01-08 |
| CN1252076C CN1252076C (en) | 2006-04-19 |
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| CN107337689A (en) * | 2017-07-13 | 2017-11-10 | 中国日用化学工业研究院 | A kind of synthetic method of alkyl phosphate monoester |
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| CN107337689A (en) * | 2017-07-13 | 2017-11-10 | 中国日用化学工业研究院 | A kind of synthetic method of alkyl phosphate monoester |
| CN107337689B (en) * | 2017-07-13 | 2020-05-05 | 中国日用化学工业研究院 | Synthesis method of alkyl phosphate monoester |
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