CN1190403C - Crystal separating-out device of bisphenol A. phenol crystal adduct, manufacture ad device thereof - Google Patents

Abstract

High purity, crystalline adduct of bisphenol A and phenol is produced multi-stage crystallization of a phenolic slurry of bisphenol A with a crystal separation and washing step being interposed between each of the two stages. Each of the crystallization stage includes a series of crystallization towers operated at decreasing temperatures. The crystallization of the slurry is performed by continuously discharging a portion of the slurry from each of the crystallization towers, introducing the discharged slurry into one or more coolers and then recycling the cooled slurry to the tower. Another portion of the slurry in each crystallization slurry is continuously discharged, heated for dissolving fine crystals of the adduct and then recycled to the crystallization tower so that large crystals are grown in each of the crystallization steps. An apparatus having a plurality of coolers and suitable for effecting the above crystallization is also disclosed.

Description

Partial crystallization device, method for making and the device thereof of dihydroxyphenyl propane phenol crystal adduct

The application is 92105365.7 divides an application, and the applying date of original application is on June 30th, 1992, application number 92105365.7, and denomination of invention is " preparation of the crystalline adduct of dihydroxyphenyl propane and phenol and process for purification, the method for making of used partial crystallization device and dihydroxyphenyl propane ".

The present invention relates to the manufacturing method and apparatus of the good higher-grade dihydroxyphenyl propane phenol crystal adduct of a kind of form and aspect, and the partial crystallization device of dihydroxyphenyl propane crystalline adduct.

People understand: if will make dihydroxyphenyl propane [2,2-two (4 '-hydroxy phenyl)] propane, then need be in the presence of acid catalyst, and acetone and excessive phenol are reacted.In addition, people also understand: if will Separation and Recovery go out highly purified dihydroxyphenyl propane from this resultant of reaction, thereby just need cool off the crystalline adduct (hereinafter to be referred as adducts) that makes it to separate out dihydroxyphenyl propane and phenol, and then from crystalline adduct, remove phenol (special public clear 36-23335 number, special public clear 62-42790 number) this resultant of reaction

Manufacture method according to this dihydroxyphenyl propane, the purity of the dihydroxyphenyl propane that is recovered as finished product and purity and the form and aspect that form and aspect depend on this crystalline adduct to a great extent thereof, so, just must produce purity high luminance relay lover's crystalline adduct if will obtain high-grade dihydroxyphenyl propane.In order from the phenol solution that contains dihydroxyphenyl propane (by what obtain after acetone and excessive phenol are reacted), to obtain high-purity crystallized adducts, must be through plural number section partial crystallization operation, and thereby the separation circuit that crystalline adduct is set therebetween forms a succession of partial crystallization operation that is connected with dissolution process, so come phenol solution is dealt with by these operations.Yet this method is also understood by people.

Make the prior art of crystalline adduct according to the partial crystallization operation of this employing complex trace, be in each section partial crystallization operation, to use a partial crystallization tower, thereby be to obtain more highly purified crystalline adduct by the hop count that increases this partial crystallization operation.Yet, in this case, if increase the hop count of partial crystallization operation, so along with the increase of partial crystallization operation hop count, also must increase the tripping device of crystalline adduct and the number of crystalline adduct dissolving tank, complicated along with partial crystallization device series, that has just produced the problem that device maximizes, installation cost rises.In addition, though can obtain highly purified crystalline adduct by the size that strengthens the partial crystallization tower, but the size of partial crystallization tower one increases, increase along with the size of partial crystallization tower, the size of crystalline adduct circulation device and micro-crystallization adducts dissolving tank also must be that exponentially ground increases, thereby can cause partial crystallization device series efficient to reduce, also produced the problem that device maximizes, installation cost is high simultaneously.

Thereby the phenol solution that contains dihydroxyphenyl propane is made the method that crystalline adduct is separated out in the partial crystallization processing as a kind of, following way can be arranged, that is: draw a part of crystalline adduct slip from the partial crystallization tower, be recycled to the partial crystallization tower with after the water cooler cooling, make the temperature of partial crystallization tower remain on the fixed partial crystallization temperature.; words according to the method; so just be difficult to the particle diameter of the crystalline adduct in the slip of gained is controlled, the size distribution of the crystalline adduct of gained will alter a great deal, and will form the crystalline adduct that contains a large amount of fine crystalline adducts particles.On the other hand, the crystalline adduct of minuteness particle shape, because its surface-area is bigger, absorption causes the material (impurity) of coloration reason easily, thereby will cause the form and aspect of the crystalline adduct of gained to degenerate.In addition, the dihydroxyphenyl propane that obtains from this crystalline adduct also can contain the material that causes coloration reason, thereby can cause the material of hue difference.So, from obtaining the viewpoint of high-grade dihydroxyphenyl propane, the phenol solution that contains dihydroxyphenyl propane is being handled when obtaining the crystalline adduct slip as partial crystallization, and important thing is will develop to produce the low crystalline adduct slip of micro-crystallization adducts particle containing ratio expeditiously.

Past, if will obtain highly purified crystalline adduct, generally be that crystalline adduct slip (obtaining by the phenol solution that contains dihydroxyphenyl propane being done the partial crystallization processing) is made filtration treatment, again the crystalline adduct of separating cleaned with high purity phenol that this is known by people.In this case, can obtain highly purified finished product crystalline adduct by the quantity that increases the partial crystallization operation.; include the crystalline adduct manufacturing processed of so much a plurality of operations; even using in each scavenging solution of the crystalline adduct that obtains in each partial crystallization operation cleaning usefulness is highly purified phenol; also be difficult to the high impurity of adsorptivity such as separating off coloring material from crystalline adduct; be difficult to obtain the very high crystalline adduct of purity; obtain a large amount of high purity phenols, can cause the raising of cost on the contrary.

In addition, words according to above-mentioned dihydroxyphenyl propane manufacture method, the purity and the form and aspect of the dihydroxyphenyl propane that is recovered as finished product obviously are purity and the form and aspect (as mentioned above) that depend on crystalline adduct to a great extent, also are subjected to a great extent the crystalline adduct that is obtained is heated influencing of condition that dissolves and the condition of this heating melt being carried out evaporation process.

From crystalline adduct, isolate phenol, generally be by evaporation, extraction, undertaken by the desorb of water vapor etc.By evaporating the method for from crystalline adduct, removing phenol, specifically on the public clear 52-42790 communique of spy disclosed, a kind of like this method is promptly arranged: after crystalline adduct is dissolved, under temperature more than 180 ℃ and reduced pressure, gasify with 0.1～30 minute time, difference condensation phenol, thus from dihydroxyphenyl propane, separate.Also having a kind of method is under 180～200 ℃ temperature crystalline adduct to be made evaporation process, does steam desorb processing (spy opens clear 63-132850 number) to having removed the later bis-phenol that contains phenol of phenol, and this method is also understood by people.Yet the form and aspect of the phenol in the crystalline adduct being made resulting dihydroxyphenyl propane after the evaporation process can variation, and its reason has been subjected to heating when being evaporation process.For example, even have the crystalline adduct of the following good form and aspect of APHA15, dissolve if be subjected to heating, so, it is just very poor that the form and aspect of the finished product dihydroxyphenyl propane of gained after the phenol have been removed in evaporation from this melt, usually at the APHA more than 40.

In order to address the above problem, people have proposed such scheme again: oxalic acid, citric acid are added in the mixture of phenol/water/dihydroxyphenyl propane, handle obtaining the dihydroxyphenyl propane (special public clear 40-19333 number) that form and aspect have been improved by distillation.In addition, in order to improve the stability of dihydroxyphenyl propane, people also know following method: add THIOGLYCOL acid, glycol acid or polyphosphoric acid (special public clear 47-43937 number); Add lactic acid, oxysuccinic acid or glycerol acid.Even but use aforesaid method, the effect of the form and aspect improvement of dihydroxyphenyl propane is still very not enough.

On the other hand, have a kind of to the dihydroxyphenyl propane that contains phenol (from crystalline adduct, remove phenol and obtain) through evaporation thus doing the steam desorb handles the method that obtains bisphenol A with high purity, like this to obtain smoking gas by separating of being formed of phenol, dihydroxyphenyl propane and steam.This separating smokes gas and will accept cooling condensation and handle, thus Separation and Recovery dihydroxyphenyl propane and phenol, but at this moment, can on the wall of water cooler, cling the solid of dihydroxyphenyl propane and phenol, thereby cause the water cooler obturation, cause the remarkable variation of cooling performance of water cooler.

One of purpose of the present invention is the process for purification that crystalline adduct will be provided.

Other purpose of the present invention is that the method for making the higher-grade crystalline adduct expeditiously will be provided.

Another other purpose of the present invention is that the method that can separate out the low higher-grade crystalline adduct of micro-crystallization adducts containing ratio (when the partial crystallization tower is separated out crystalline adduct) will be provided.

Another other purpose of the present invention is that the method that goes out the higher-grade adducts from crystalline adduct slip Separation and Recovery will be provided.

Another other purpose of the present invention is that the partial crystallization that can separate out higher-grade crystalline adduct device will be provided.

Another other purpose of the present invention be to provide a kind of and can obtain that form and aspect are good, painted, high-grade dihydroxyphenyl propane of no melt (from crystalline adduct when evaporation is removed wherein contained phenol and made dihydroxyphenyl propane).

Another other purpose of the present invention be to provide a kind of can prevent because of dihydroxyphenyl propane method of colouring that evaporation heating is caused (from crystalline adduct when evaporation is removed wherein contained phenol and is made dihydroxyphenyl propane.

Another other purpose of the present invention is that a kind of method (this is the method for using when making dihydroxyphenyl propane by following operation) that can obtain the higher-grade dihydroxyphenyl propane expeditiously will be provided, and described operation is: remove wherein contained phenol through evaporation from the phenol solution that contains dihydroxyphenyl propane; To containing the dihydroxyphenyl propane of the phenol that obtains from this phenol evaporization process, the operation of carrying out the steam desorb.

Another other purpose of the present invention is that a kind of desorption gas (obtaining when the dihydroxyphenyl propane that contains phenol is done the desorb processing) is carried out condensation under the situation that does not fold solid state dihydroxyphenyl propane and phenol method will be provided.

In order to achieve the above object, the present inventor has carried out research with keen determination, and the result has finished the present invention finally.

Can provide a kind of manufacture method of refining phenol by the present invention, it is characterized in that making the industrial phenol of moisture below 0.5Wt% to contact, under the temperature below 185 ℃, distill processing then with strong acid ion exchange resin.

By the present invention, can provide with following item as the 1st process of making crystalline adduct is the manufacture method of the dihydroxyphenyl propane phenol crystal adduct of feature:

Be admitted to the phenol solution that has dissolved dihydroxyphenyl propane in the 1st partial crystallization tower (A) in 2 partial crystallization towers that connecting for the polyphone of implementing the 1st section partial crystallization operation, separate out the kind crystalline substance that is constituted by the dihydroxyphenyl propane phenol crystal adduct, meanwhile, the crystalline adduct slip that contains resulting kind crystalline substance in this partial crystallization operation is sent into the 2nd partial crystallization tower (B), under the temperature that is lower than above-mentioned the 1st partial crystallization tower A, this kind crystalline substance is implemented crystalline growth, after handling like this, again the crystalline adduct slip that obtains in the 1st section partial crystallization operation is sent into solid-liquid separation process, thereby from mother liquor, isolate crystalline adduct, then the phenol that is higher than mother liquor with purity again dissolves this crystalline adduct again, and then send into to implementing the 2nd section partial crystallization operation, the 1st partial crystallization tower (C) in 2 partial crystallization towers that connecting, separate out the kind crystalline substance that crystalline adduct constituted by dihydroxyphenyl propane phenol, meanwhile, resulting crystalline adduct slip in this partial crystallization operation is sent into the 2nd partial crystallization tower (D), with the temperature that is lower than the 1st partial crystallization tower (C) the brilliant crystalline growth of implementing of above-mentioned kind is handled again.

By the present invention, as the 2nd process of making crystalline adduct, can provide with following item is the manufacture method of the dihydroxyphenyl propane phenol crystal adduct of feature; On the basis of the method for having used the individual partial crystallization tower of n (n 〉=2) (having the inner core that is provided with opening portion on top) manufacturing dihydroxyphenyl propane phenol crystal adduct,

(a) in each partial crystallization tower, make it to separate out the dihydroxyphenyl propane phenol crystal adduct, thereby form the crystalline adduct slip;

(b) draw the crystalline adduct slip from the interior tube bottom of each partial crystallization tower;

(c) part of each crystalline adduct slurry of drawing is cooled off, each partial crystallization tower is sent in circulation then;

(d) in the partial crystallization tower of the 1st～the n section, draw the crystalline adduct slip from the partial crystallization tower of n section at least, part to this slip heats, again micro-crystallization adducts particle contained in this crystalline adduct slip is dissolved, and then this partial crystallization tower is sent in circulation;

(e) be circulated to the 1st section partial crystallization tower, be added into by the stock liquid that phenol solution constituted that contains dihydroxyphenyl propane in the chilled crystalline adduct slip, send into the 1st section partial crystallization tower then;

(f) since the 1st section, after being added to, the part of the crystalline adduct slurry of drawing from the interior tube bottom of each partial crystallization tower of (n-1) section goes the circulating cooling pipe road of the crystalline adduct slip of each partial crystallization tower, thereby after being sent in the partial crystallization tower of each section;

(g) part of the circulation slip that has been heated the part of the crystalline adduct slip that tube bottom is drawn in the partial crystallization tower of n section or the n section is recovered as finished product crystalline adduct slurry.

By the present invention, as the 3rd process of making crystalline adduct, can provide with following item is the manufacture method of the dihydroxyphenyl propane phenol crystal adduct slip of feature:

Its top of insertion is provided with the inner core of opening portion in the urceolus of closed structure, send into the phenol solution that contains dihydroxyphenyl propane in the urceolus of the partial crystallization tower of 2 weight structures, meanwhile, draw dihydroxyphenyl propane phenol crystal adduct slip from the interior tube bottom of this partial crystallization tower, part to this crystalline adduct slip of having drawn heats, by the time in this crystalline adduct slip contained micro-crystallization adducts particle dissolved after, again from this urceolus bottom, make it to form with the unidirectional cycle stream of above-mentioned crystallisation by cooling adducts slip and circulate by this way and deliver in the urceolus, meanwhile, a part of drawing from the crystalline adduct slip of interior tube bottom is reclaimed as finished product crystalline adduct slip, or the part of the crystalline adduct slip after micro-crystallization adducts particle contained in this crystalline adduct slip dissolved is reclaimed as finished product adducts slip.

By the present invention, as the 4th process of making crystalline adduct, can provide with following item is the manufacture method of the dihydroxyphenyl propane phenol crystal adduct of feature:

Be ready to partial crystallization tower and water cooler, draw the part of crystalline adduct slip also cools off with this water cooler from this partial crystallization tower, by cooled crystalline adduct slurry recycle to this partial crystallization tower, thereby in the partial crystallization tower, separate out crystalline adduct, the crystalline adduct of separating out is drawn and separated from the crystalline adduct slip from this partial crystallization tower, on the basis of above-mentioned crystal method, be set up in parallel a plurality of above-mentioned water coolers, a standby water cooler is arranged in a plurality of water coolers, only use standby water cooler water cooler in addition that the crystalline adduct slip is cooled off, separated out crystalline adduct at heat-transfer surface, water cooler and standby water cooler that heat transfer efficiency has descended exchange, thereby carry out operate continuously, meanwhile, heat to dissolve by the water cooler that heat transfer efficiency descended and paying in the crystalline adduct of heat-transfer surface and regenerate.

By the present invention, as the 5th process of making crystalline adduct, can provide with following item is the manufacture method of the dihydroxyphenyl propane phenol crystal adduct of feature:

Comprise: the phenol solution that contains dihydroxyphenyl propane, the partial crystallization operation of n (n 〉=2) section, the solid-liquid separation process of n section, at least the crystalline adduct that contains one section dihydroxyphenyl propane phenol crystal adduct matting and n-1 section is dissolution process again, since the 1st section, the partial crystallization resultant that is obtained in each section partial crystallization operation of n-1 section is made solid-liquid separation, crystalline adduct to gained does not deal with or cleans with scavenging solution, dissolve once more with phenol solution then and send into later partial crystallization operation, and the partial crystallization resultant that obtains in the partial crystallization operation to the n section is made solid-liquid separation, resulting crystalline adduct is cleaned with scavenging solution, thereby obtain highly purified crystalline adduct, on a kind of like this basis of method

(a) in the solid-liquid separation process of n section, use refining phenol at least a portion of the scavenging solution of resulting the n time crystalline adduct;

(b) in the solid-liquid separation process of the n-1 section, use the cleaning discharge opeing of the crystalline adduct that is obtained in the solid-liquid separation process of n section at least at least a portion of dissolving again of resulting crystalline adduct, perhaps use the mother liquor that obtains in the solid-liquid separation process of n section with phenol solution;

(c) use the cleaning discharge opeing of the crystalline adduct that is obtained in the solid-liquid separation process of the mother liquor that obtained in the solid-liquid separation process of n section or n section at least a portion of the scavenging solution of the crystalline adduct that in the solid-liquid separation process of at least the n-1 section, obtains;

(d) from the 1st section crystalline adduct to each section of n-1 section dissolve again impurity (impurity) concentration in the phenol solution of usefulness and the impurity concentration in the crystalline adduct scavenging solution all be higher than after one section the crystalline adduct concentration of dissolving impurity in impurity concentration in the phenol solution of usefulness and the crystalline adduct scavenging solution again.

By the present invention,, can provide the manufacture method of bis-phenol crystalline adduct with following feature as the 6th process of making crystalline adduct:

The phenol solution that contains dihydroxyphenyl propane is analysed the dihydroxyphenyl propane phenol crystal adduct slip that obtains after the processing when carrying out filtration treatment do crystallization, in this crystalline adduct, a part that makes the micro-crystallization adducts composition of particle diameter below 100 μ m is towards the filtration side shifting, thereby the recovery particle diameter becomes the thick crystalline adduct of ratio below 20 weight % of branch at the micro-crystallization adducts below the 100 μ m.

By the present invention, as the partial crystallization device of making crystalline adduct, it is the manufacturing installation of the dihydroxyphenyl propane phenol crystal adduct of feature that following array structure can be provided:

This device has partial crystallization tower and a plurality of water cooler, the position of this partial crystallization tower beyond its bottom is provided with the inlet that returns of crystalline adduct slip, be provided with the outlet of crystalline adduct slip in its bottom, each water cooler is respectively equipped with entrance and exit, between the inlet of the outflow of the crystalline adduct slip of partial crystallization tower and water cooler, and between the outlet of returning inlet and water cooler of crystalline adduct slip respectively the handover means by the crystalline adduct slip realize being connected, the crystalline adduct slip exports optionally by water cooler (getting rid of any one from a plurality of water coolers) from the crystalline adduct pulp flow of this partial crystallization tower, and the returning of crystalline adduct slip that is transferred to the partial crystallization tower then enters the mouth.

By the present invention, as the 1st process that obtains dihydroxyphenyl propane, can provide with following item is the manufacture method of the higher-grade dihydroxyphenyl propane of feature:

By dihydroxyphenyl propane and phenol constitute, to dissolve look APHA be crystalline adduct below 15, that be in neutrallty condition in fact is heated under the concentration of oxygen is gas condition below the 0.05VOL% and dissolves for it, meanwhile, from acquired melt, remove phenol through evaporation.

By the present invention.As the 2nd process that obtains dihydroxyphenyl propane, can provide with following item is feature, the manufacture method of higher-grade dihydroxyphenyl propane:

The mixture that contains crystalline adduct (be made of dihydroxyphenyl propane and phenol, it dissolves look APHA is below 15, in fact is in neutrallty condition) and aliphatic carboxylic acid is heated under 130～200 ℃ temperature condition, and evaporates by reducing pressure and to remove phenol.

By the present invention, as the 3rd process that obtains dihydroxyphenyl propane, can provide with following item is the manufacture method of the higher-grade dibit phenol A of feature:

Constitute by dihydroxyphenyl propane and phenol, contain the strongly-acid material and be under the solutions of weak acidity, to dissolve look APHA be in the crystalline adduct below 15 for it, with in the strongly-acid material in this crystalline adduct and a great deal of add to mix the people aliphatic carboxylate, under 130-200 ℃ temperature and reduced pressure, remove phenol then through evaporation.

By the present invention, as the 4th process that obtains dihydroxyphenyl propane, can provide with following item is the manufacture method of the higher-grade dihydroxyphenyl propane of feature:

The crystalline adduct that dissolves look APHA and be dihydroxyphenyl propane below 15 and phenol is sent to and is provided with the device series that dissolves device and evaporation unit, dissolve device by this and dissolve crystalline adduct, by this evaporation unit the crystalline adduct dissolution liquid is made evaporation process, thereby dihydroxyphenyl propane and phenol are reached to be separated from each other, on the basis of aforesaid method, by the cleaning of organic solvent, included in this device series be above-mentionedly to dissolve within device and the evaporation unit in the wall accompanying amount of oxygen and remove at least to inner-wall surface 1m ²Less than the such degree of 10 mmoles, then crystalline adduct is delivered to said apparatus series, thereby dissolve and evaporation process.

By the present invention, as the 5th process that obtains dihydroxyphenyl propane, can provide with following item is the manufacture method of the higher-grade dihydroxyphenyl propane of feature:

Use a kind of like this evaporator tower, that is: can be that the dissolution liquid of the crystalline adduct of dihydroxyphenyl propane below 15 and phenol is delivered to its inside and is provided with and makes parts that evaporation surface improves and by evaporation process that at least one evaporator tower constituted dissolving look APHA, remove phenol through evaporation under reduced pressure, removed to 1m in advance at the inner-wall surface of this evaporator tower and at the oxygen that this evaporator tower adhering on surface inner set, that be the parts of raising evaporation surface this moment ²Surface-area be below 10 mmoles.

By the present invention, as the 6th process that obtains dihydroxyphenyl propane, can provide with following item is the manufacture method of the higher-grade dihydroxyphenyl propane of feature.

At first be the phenol evaporization process: from the dihydroxyphenyl propane phenol crystal adduct when evaporation is removed phenol and is obtained dihydroxyphenyl propane, adopt thin-film evaporator under the pressure of 160-180 ℃ temperature and 15-60 holder, the phenol solution that contains dihydroxyphenyl propane (forming from this crystalline adduct) is carried out evaporation process, is the dihydroxyphenyl propane of 1-5 weight % thereby obtain phenol content; Next comprises that the 1st separates operation: under the following pressure of 170-185 ℃ temperature and 151 holders, make the dihydroxyphenyl propane that contains phenol (obtaining) in above-mentioned phenol evaporization process smoke gas and do that subtend is mobile to be contacted with separating, thereby carry out the desorb processing; Comprise the 2nd desorption step again: under the pressure of 170-185 ℃ temperature and 15 holders, make the dihydroxyphenyl propane that contains phenol (in the 1st desorption step, obtaining) smoke that the gas subtend is mobile to be contacted with separating; In the 2nd desorption step, be steam as separating what smoke gas, as separating in the 1st desorption step smoke gas be to use by contain phenol and dihydroxyphenyl propane (obtaining in the 2nd desorption step) steam constituted separates and smoke gas.

By the present invention, as the 7th process that obtains dihydroxyphenyl propane, can provide with following item is feature, the manufacture method of higher-grade dihydroxyphenyl propane:

At first be the phenol evaporization process: adopt thin-film evaporator, aerial oxygen concn is under the condition of 0.005Vol%, again under the pressure of 160-185 ℃ temperature and 15-60 holder, to contain dihydroxyphenyl propane (from be in fact neutrallty condition, dissolve form the dihydroxyphenyl propane phenol crystal adduct of look below 15APHA) phenol solution make evaporation process, be the dihydroxyphenyl propane of 1-5 weight % thereby obtain phenol content; Next comprises the 1st desorption step: under the pressure of 170-185 ℃ temperature and 15 holders, make the dihydroxyphenyl propane that contains phenol (in above-mentioned evaporization process, obtaining) smoke gas and make subtend and flow and contact with separating, thus realization desorb processing; Smoke gas as separating of the 2nd desorption step and be to use steam, as separating of the 1st desorption step smoke gas be to use by contain phenol and dihydroxyphenyl propane (in the 2nd desorption step, obtaining) steam constituted separates and smoke gas.

By the present invention, as the 8th process that obtains dihydroxyphenyl propane, can provide with following item is the condensation processing method of the desorption gas of feature:

To contain phenolic compound (what the mixing solutions of phenol and dihydroxyphenyl propane is done obtain when the steam desorb is handled) under the low pressure condition of 30 holders, dihydroxyphenyl propane and steam separate the method that gas carries out condensation process that smokes, also having the 1st refrigerating work procedure on the basis of this method: under the low pressure condition below 30 holders, and make steam remain the gas shape and the part of phenolic compound is remained under the liquid temperature condition, make this desorption gas and the 1st heat-eliminating medium (by phenol or contain dihydroxyphenyl propane phenol constituted) make subtend and flow and to contact, when the part of whole in fact amount of contained dihydroxyphenyl propane and phenol is accepted condensation in making this desorption gas, can obtain the mixed gas of uncooled steam and phenol; Comprise the 2nd refrigerating work procedure again: under the low pressure condition below 30 holders and make under the temperature condition of whole in fact amount condensations of this mixed gas, make the above-mentioned mixed gas that obtains in the 1st refrigerating work procedure and the 2nd heat-eliminating medium (aqueous solution by phenol is constituted) make subtend and flow and contact, thereby make whole in fact amount of this mixed gas obtain condensation.

Below, will the process for purification of crystalline compounds of the present invention be described in detail.

According to the manufacture method of crystalline adduct of the present invention, be that the crystalline adduct of dihydroxyphenyl propane and phenol is implemented (i) industrial phenol; The (ii) reaction process of phenol and acetone; The (iii) enrichment process of resultant of reaction; (iv) use and a kind ofly make clean by the refining phenol of specific method purified (raw material of described refining phenol is: at least a phenol of selecting in the resulting phenol from the cleaning process of the adducts of the partial crystallization operation of the phenol that contains dihydroxyphenyl propane).Present inventors, in order to obtain to be suitable for crystalline adduct is done the phenol of cleaning, process for purification with regard to above-mentioned phenol itself has carried out research with keen determination, the result finds finally: this phenol is contacted after distill the sort of material that causes coloration reason that the refining thing of handling resulting phenol does not contain the form and aspect reduction that makes the finished product dihydroxyphenyl propane with strong acid ion exchange resin, with this refining phenol crystalline adduct is cleaned, the finished product dihydroxyphenyl propane that obtains after the crystalline adduct of cleaning is removed phenol is the material that a kind of form and aspect are extremely excellent, tint permanence is very low.

In the present invention, being used for the phenol that crystalline adduct do to be cleaned is refining thing from the selected at least a phenol of following material, they are (i) industrial phenol, the (ii) phenol of from the resultant of reaction of phenol and acetone, separating, (iii) the phenol of from the crystal resultant of the phenol that contains bis-phenol, separating and (iv) crystalline adduct has been done to clean after finished the phenol that uses.

As industrial phenol, commercially available, the product of phenol purity more than 99.5 weight % arranged, but in the present invention, can use the refining thing of this phenol.Through the resulting resultant of reaction of reaction of phenol and acetone, owing to wherein contained resultant dihydroxyphenyl propane is concentrated, will from this resultant of reaction, isolate phenol, but can use the refining thing of this phenol that has separated in the present invention.

In addition, thereby handle and to separate out under the occasion of crystalline adduct the phenol that contains dihydroxyphenyl propane being made partial crystallization, normally adopt the partial crystallization operation of plural number section and the solid-liquid separation process of partial crystallization resultant, just obtained plural kind of mother liquor (phenol) thereupon, but can use in the present invention, the refining thing of the phenol that can form these mother liquors.The refining thing of employed mother liquor can be the refining thing of any mother liquor in these mother liquors among the present invention, but preferably uses the refining thing of the mother liquor of separating from partial crystallization resultant (obtaining the partial crystallization operation of leading portion).

In the present invention, although the phenol that can obtain finishing to use after crystalline adduct do is cleaned in the present invention, also can use the refining thing of the phenol that this end used effectively.

In order to obtain the refining thing of above-mentioned phenol used in the present invention, as producing the used raw material phenol of this refining thing, generally its purity is preferably used the phenol of 99.5 weight % more than 99 weight %.

When phenol refining, at first be to use phenol to contact processing, but at this moment sulfone styrene diethylene benzene copoly mer, sulfone crosslinked styrene polymers, phenol-aldehyde-sulfone acid resin, benzene-formaldehyde-sulfone acid resin etc. arranged as strong acid ion exchange resin with strong acid ion exchange resin as raw material.These resins all have crosslinking structure, are insoluble substances.The gel-type material is arranged in this strong acid ion exchange resin, big porous material, this is understood by people.But in the present invention, can use above-mentioned any material, yet, the gel-type material preferably used.Big porous material is different with the gel-type material, when using as catalyzer, often is to demonstrate lower activity, does not therefore preferably use.Concerning the strong acid ion exchange resin of gel-type, its degree of crosslinking (weight of contained linking agent in the resin) should be below 10%, preferably below 5%.Can enumerate as Rohm﹠amp as the strong acid ion exchange resin of employed gel-type preferably among the present invention; The Combe, George Alexander of Hass company draws special ion exchange resin (Amberlite) and Combe, George Alexander Li Site ion exchange resin (Amberlyst); Mitsubishi changes into the Di Aweng ion exchange resin (DIAION) of company.Can implement by the following method when using this strong acid ion exchange resin that phenol is handled: the method that in containing the packed tower of strong acid ion exchange resin (packing tower), phenol is flow through; Put into phenol at the steel basin of having put into strong acid ion exchange resin and carry out stirring method.Treatment temp is 45-150 ℃, is preferably 50-100 ℃.Be 5-200 minute the duration of contact of strong acid ion exchange resin and phenol, is preferably 15-60 minute.When with this strong acid ion exchange resin phenol being handled, the moisture content in the phenol is preferably in below 0.1 weight below 0.5 weight %.When moisture content surpassed this scope, the effect of the conversion of the impurity (impurity) that is undertaken by strong acid ion exchange resin will variation.To from phenol, remove moisture content to 0.5 weight %, can in phenol, add and realize by azeotropic for the known entrainer of people.

With the phenol that above-mentioned strong acid ion exchange resin contacts, contain the material of the high-boiling-point impurity that impurity transformed, handling by distillation can be this high-boiling-point impurity as residual the checking the mark from coming out of distillation.

The transhipment condition of distillation tower is phenol and high-boiling-point impurity to be separated get final product, but must accomplish: do not sneak into high-boiling-point impurity in distilled phenol, the thing that should note is that the temperature that distillation is handled remains on below 185 ℃.When the temperature below 185 ℃, running pressure can be set arbitrarily, but under the decompression of 50-600 holder, carry out usually.When operating temperature surpasses 185 ℃, will cause the decomposition of high-boiling-point impurity, thereby the downgrade of feasible refining phenol, so be worthless.

By the refining phenol that above-mentioned processing obtained, its APHA benchmark form and aspect are below 10, even therefore attached to being on the dihydroxyphenyl propane of finished product, also can not cause degenerating of form and aspect.

The cleaning of the crystalline adduct of being undertaken by refining phenol, the method that can use crystalline adduct and refining phenol fully to contact.This clean for example can be removed mother liquor earlier from crystalline adduct in the equipment for separating liquid from solid that is the filtration machinery of fractional crystallization adducts and separating centrifuge etc., thereby then cleaning in the refining phenol introducing equipment for separating liquid from solid.Also can come row is made clean from the accompanying crystalline adduct of a spot of mother liquor of equipment for separating liquid from solid by refining phenol with other steel basin.The usage ratio that is used for the refining phenol of crystalline adduct is: the crystalline adduct to per 100 weight unit is the 30-1000 weight unit, preferably the 100-300 weight unit.

Be subjected to the crystalline adduct of clean by above-mentioned refining phenol, its surface attachment is made with extra care phenol.This material is sent in the operation of removing phenol from crystalline adduct, removes phenol there, thereby reclaims the dihydroxyphenyl propane of high purity goods.Remove phenol from crystalline adduct, the existing known method of people, for example: methods such as evaporation, extraction, steam desorb.

With the process for purification of crystalline adduct of the present invention, can obtain the product dihydroxyphenyl propane form and aspect excellence, that tint permanence is low.In the present invention, as the scavenging solution of crystalline adduct, if use the refining thing of specific phenol, then just can obtain following advantage point.

(1) owing to do not sneak into impurity in the adducts that is obtained, especially do not sneak into the impurity that causes coloration reason, therefore can obtain finished product dihydroxyphenyl propane purity height and form and aspect excellence, that tint permanence is low.

(2) do not sneak into solvent owing in the scavenging solution, so can intactly recycle scavenging solution in reaction train or partial crystallization series.

Employed in the present invention refining phenol, refer to as top, scavenging solution as the crystalline adduct of phenol and dihydroxyphenyl propane is well suited for, because be a kind of highly purified material of form and aspect excellence, if rank biology as the good various phenol of form and aspect, the manufacturing raw material of alkylphenol and phenol resins for example, that also is well suited for.

In addition, in the refining phenol that the present invention obtained,, can suppress to store and the form and aspect when reacting reduce by adding the oxalic acid and the citric acid of a small amount of (0.0001-0.001 weight %).

Below, the manufacture method of crystalline adduct of the present invention is illustrated.(the 1st process)

Fig. 1 has shown the system diagram for the device of the 1st process of making crystalline adduct of the present invention.In the figure, A, B, C, D represent the partial crystallization tower, and E represents equipment for separating liquid from solid, and F represents dissolving tank.

Within each partial crystallization tower A, B, C, D, insert and to have disposed the inner core P that its top is provided with peristome.In addition, in each partial crystallization tower A, B, C, D, set up the dissolving vessel of micro-crystallization adducts.Partial crystallization tower A and the B connection of being contacted, thus constituted for implementing the device series of the 1st section partial crystallization operation, and partial crystallization tower C and D are also connected by polyphone, thereby have constituted for implementing the device series of the 2nd section partial crystallization operation.

Contain phenol solution, be supplied to the bottom of the 1st partial crystallization tower A among 2 partial crystallization tower A, the B that connecting by pipeline 1 and pipeline 2, separate out the kind crystalline substance that constitutes by dihydroxyphenyl propane, phenol crystal adduct here as the dihydroxyphenyl propane of processed raw material.In this partial crystallization tower A, the phenol solution that contains the crystalline adduct (planting brilliant) of tower internal upper part flows down along inner core P, led to the outside by pipeline 3, be circulated to the inside of the 1st partial crystallization tower A again by pump 4, pipeline 5 and water cooler 6 and pipeline 2, so, phenol solution in the partial crystallization tower A has just obtained cooling, partial crystallization tower A just be cooled to fixed temperature.

The crystal resultant that contains kind of a crystalline substance (the inner core P in partial crystallization tower A draws), promptly the part of crystalline adduct slip at this moment (being called slip by tube) is by pipeline 7, pump 8, pipeline 9, pipeline 10 and well heater 11 are introduced into micro-crystallization adducts dissolving vessel Q, here, fine crystalline in the crystalline adduct is dissolved, the brilliant slip of kind that only contains the even thick crystallization of determining of size is circulated to the bottom of partial crystallization tower A by pipeline 13, so the particle diameter of the inner contained kind crystalline substance of partial crystallization tower A is become evenly, in partial crystallization tower A, so it is lower just to have generated the brilliant containing ratio of the kind of micro-crystallization, the higher kind crystalline substance of the brilliant containing ratio of thick crystalline kind.

Micro-crystallization adducts in the partial crystallization tower A, its surface-area is bigger, and the material that constitutes coloration reason has been shown higher adsorptivity.So the particle containing ratio of the micro-crystallization composition in the crystalline adduct that obtains as kind of crystalline substance among the partial crystallization tower A is reduced significantly, and then has obtained the good kind crystalline substance of form and aspect.According to present inventors' research, the particle containing ratio of the micro-crystallization composition in the crystalline adduct below the particle diameter 100 μ m should preferably remain on below the 20 weight % below 30 weight %, so just can produce the crystalline adduct that form and aspect are good, purity is high.

In the present invention, the phenol solution that contains dihydroxyphenyl propane (using as processed raw material) is normally formed in following ratio: dihydroxyphenyl propane is 7-50 weight %, and 10-30 weight % preferably is as the metamer that dihydroxyphenyl propane is arranged of other compositions, triphenols etc., its ratio is below 8 weight %.

The temperature that contains the phenol solution of the dihydroxyphenyl propane of coming from transfer limes 1 exceeds 1-20 ℃ than the temperature of saturation of crystalline adduct.The partial crystallization temperature of partial crystallization tower A is 45-70 ℃, is preferably 48-57 ℃.The slip that is recycled by pipeline 3, pump 4, water cooler 6 and pipeline 2 reduces to below 10 ℃ its temperature by water cooler 6, preferably reduces to below 5 ℃.The residence time of phenol solution in partial crystallization tower A is 0.5-10 hour, is preferably 0.5-5 hour.

On the other hand, send into the slip of micro-crystallization adducts dissolving vessel Q,, make 0.5-5 ℃ of its temperature rising by well heater 11 by pipeline 7, pump 8, pipeline 10, well heater 11.The residence time of phenol solution in this jar Q is 3-15 minute.

In the micro-crystallization dissolving vessel, mainly be that the following micro-crystallization adducts of particle diameter 100 μ m is dissolved, the slip that this micro-crystallization adducts is dissolved is returned to partial crystallization tower A by pipeline 13, in partial crystallization tower A, promote the crystalline growth, thereby obtained thick crystalline kind crystalline substance.

The some of the slip that draw the bottom of the inner core P in the 1st partial crystallization tower A is introduced into the bottom of the 2nd partial crystallization tower B by pipeline 7, pump 8, pipeline 12 and pipeline 21, realizes the growth of crystalline adduct here.The working method of this 2nd partial crystallization tower B is the same with the working method of above-mentioned partial crystallization tower A.

In partial crystallization tower B, its temperature range is 45-70 ℃, remains on than the partial crystallization temperature of partial crystallization tower A to hang down about 3-10 ℃.Through the slip of supercooler 26, its temperature is dropped to about 10 ℃, preferably reduce to below 5 ℃.

On the other hand, by the slip of well heater 31, make 0.5-5 ℃ of its temperature rising here.

In the micro-crystallization adducts dissolving vessel Q in being arranged on partial crystallization tower B, crystalline adduct composition below the particle diameter 100 μ m is dissolved, the slip that the micro-crystallization adducts is dissolved is sent back to the partial crystallization tower through pipeline 33, thereby promoted this crystalline to grow up, the concentration of the crystalline adduct the slip that draw the bottom of the inner core P in partial crystallization tower B is 35 weight %, be preferably 25 weight %, in its crystalline adduct particle diameter be the containing ratio of particle of the following micro-crystallization composition of 100 μ m below 30 weight %, be preferably in below the 20 weight %.

The part of the slip of drawing from the bottom of the inner core P of the 2nd partial crystallization tower B is through pipeline 35 and be introduced into equipment for separating liquid from solid E, realize separating of crystalline adduct and mother liquor here, the crystalline adduct that is separated is admitted to the crystalline adduct dissolving tank by pipeline 36 again, so realize dissolving more here.

As equipment for separating liquid from solid E, known for everybody, separating centrifuge, filtration unit etc. are for example arranged.As dissolving tank E, also have knownly for people, for example there is its inside to be provided with the steel basin of agitator and the dissolving tank of hot type.

In dissolving tank E, at first be to introduce refining phenol from pipeline 81, use then and should make with extra care phenol, preferably under stirring condition, make crystalline adduct obtain alkene and release dissolving.At this moment, can be as required simultaneously also with heating, the temperature of dissolving tank is 70-160 ℃, is preferably 80-100 ℃.Its purity that is to use as refining phenol is higher than the material of mother liquor.

With refining phenol crystalline adduct is being carried out alkene when releasing dissolved, as this refining phenol, if do not constitute the words of material coloration reason, that the impurity containing ratio is few of finished product dihydroxyphenyl propane, that just has no particular limits, the refining phenol of in the present invention fit for service can be enumerated various refining phenol related in the process for purification of above-mentioned crystalline adduct.

Refining phenol like this, the form and aspect of its APHA benchmark are below 10, even attached on crystalline adduct and the product dihydroxyphenyl propane time, also not conference makes its form and aspect variation.

Contain the phenol solution from the dihydroxyphenyl propane of dissolving tank, process pipeline 41 is sent to the bottom of the 1st partial crystallization tower that constitutes the 2nd section partial crystallization system, the phenol solution of this moment, and the concentration of its dihydroxyphenyl propane is 7-50 weight %, is being well the concentration that is adjusted to 10-30 weight %.

This partial crystallization tower C is according to operating with the identical mode shown in the above-mentioned partial crystallization tower A.In partial crystallization tower C, its partial crystallization temperature is 45-70 ℃, is maintained on 0-10 ℃ the temperature that exceeds partial crystallization tower A.By the slip of water cooler 46, here make below its temperature drops to about 10 ℃, preferably drop to about 5 ℃ below.

On the other hand, by the slip of well heater 51, make 0.5-5 ℃ of its temperature rising here.

In the micro-crystallization adducts dissolving vessel Q in being arranged on partial crystallization tower C, the following micro-crystallization composition of particle diameter 100 μ m is dissolved, and the slip that the micro-crystallization composition is dissolved is returned to partial crystallization tower C by pipeline 53, thereby promotes crystalline to grow up.

The part of the slip that draw the bottom of the inner core P in the partial crystallization tower C by pipeline 52, pipeline 61 and pipeline 62, be sent to the bottom of the 2nd partial crystallization tower D that constitutes the 2nd section partial crystallization system, realize that here crystalline grows up.

The 2nd partial crystallization tower D is according to operating with the same method shown in the above-mentioned partial crystallization tower A.In partial crystallization tower D, its partial crystallization temperature is 45-70 ℃, and the temperature that is kept exceeds about 0-10 ℃ than partial crystallization tower C, and also exceeds about 0-10 ℃ than partial crystallization tower B.

On the other hand, by the slip of well heater 71, make about 0.5-5 ℃ of its temperature rising here.

In the dissolving vessel Q of the micro-crystallization adducts in being arranged on partial crystallization tower 0, the micro-crystallization adducts composition below the particle diameter 100 μ m is dissolved, and the dissolved slip of micro-crystallization composition is sent back to the partial crystallization tower by pipeline 73, realizes the crystalline growth here.From the slip that draw the bottom of the inner core P of partial crystallization tower D inside, the concentration of its crystalline adduct is 35 weight %, be preferably 25 weight %, it is below the 30 weight % that the micro-crystallization adducts in this crystalline adduct below the particle diameter 100 μ m becomes the containing ratio of branch, is preferably below the 20 weight %.

The slip that draw the bottom of inner core P in the partial crystallization tower D is retracted as the product slip through pipeline 80.In case of necessity, can implement solid-liquid separation to this slip, resulting crystalline adduct is sent to the recovery process of dihydroxyphenyl propane, has removed phenol afterwards with regard to recyclable dihydroxyphenyl propane.

According to the present invention,, just can higher yield obtain purity height, APHA at the good dihydroxyphenyl propane phenol crystal adduct of the form and aspect below 15 by for obtaining the 1st process of crystalline adduct.

This dihydroxyphenyl propane phenol crystal adduct by from removing phenol here, just can obtain purity high luminance relay lover's dihydroxyphenyl propane.

(the 2nd process)

Below, will to of the present invention, for obtaining the 2nd process of crystalline adduct, under the situation of reference drawing, describe.

Fig. 2 has shown by using 2 (n=2) partial crystallization towers to implement plant system drawing of the present invention.In the figure, A represents the 1st section partial crystallization tower, and B represents the 2nd section partial crystallization tower.

Each partial crystallization tower A, B, all portion inserts and to have disposed the inner core P that its top is provided with opening within it.In addition, in each partial crystallization tower A, B, also be provided with micro-crystallization adducts dissolving vessel Q.

In each partial crystallization tower A, B of running well, crystalline adduct has been separated out in its inside, so formed the slip of crystalline adduct.In addition, the crystalline adduct slip is directed to the outside from the bottom of the inner core P of each partial crystallization tower A, B through pipeline 3,23, some wherein is by each pump 4,24, pipeline 5,25 and water cooler 6,26, and be circulated to by pipeline 2,22 and be equipped with in partial crystallization tower A, the B, so, slip in partial crystallization tower A, the B is cooled off, each partial crystallization tower A, B just be cooled to fixed temperature.

In addition, contain crystalline adduct (from each partial crystallization tower A, inner core P in the B draws) the part of slip, through pipeline 7,27, pump 8,28, pipeline 9,29, pipeline 10,29 and well heater 11,31 are admitted to micro-crystallization adducts dissolving vessel Q, here, fine crystalline particle in the crystalline adduct is dissolved, the slip that contains the thick crystalline adduct of uniform-dimension passes through pipeline 13,33, and be circulated to partial crystallization tower A, the bottom of B, so, partial crystallization tower A, the particle diameter of contained crystalline adduct has formed unanimity in the B, at partial crystallization tower A, among the B, the containing ratio that has formed micro-crystallization adducts particle is lower, the higher crystalline adduct of thick crystalline adduct particle containing ratio.With dissolving vessel Q this crystalline adduct slip is carried out after the dissolution process, the operation that is circulated in the partial crystallization tower has only been carried out just at terminal section, if necessary, also can save this operation at other partial crystallization tower.

Micro-crystallization adducts in partial crystallization tower A, the B, its surface area ratio is bigger, and the material that causes coloration reason has been shown higher adsorptivity.Therefore, by the containing ratio of the micro-crystallization adducts particle in the crystalline adduct (obtaining among partial crystallization tower A, the B) is done to reduce as far as possible, so just can obtain the good crystalline adduct of form and aspect.Research according to present inventors can be known: remain under the 30 weight % at the containing ratio of the micro-crystallization adducts particle below the 100 μ m by making the particle diameter in the crystalline adduct, preferably remain on 20 weight %, just can obtain the crystalline adduct that form and aspect are good, purity is high.

The slip that descended through the temperature of pipeline 2,22 and be recycled by the slip that pipeline 13,33 temperature have risen is sent in partial crystallization tower A, the B, at this moment, just forms in the urceolus unidirectional cycle from the urceolus bottom of partial crystallization tower A, B and flows.At this moment, preferably, introduce by tangential direction, and should make the position of introducing different facing to the inner peripheral surface of urceolus.In addition, the introducing position of these 2 kinds of slips is to represent with angle from the central point of urceolus, can be undertaken by the isolating position of 90-180 degree.Moreover owing to produced unidirectional cycle stream, the introducing position of 2 kinds of slips not necessarily will be maintained at the same horizontal plane, and deviation more or less just also is not form what obstruction in the bottom of urceolus.

As mentioned above, introduce (its incoming direction should form tangent line with the inner peripheral surface of crystal tower A, B) in partial crystallization tower A, the B by each slip of pipeline 2,22 and pipeline 13,33, when making the slip formation cycle stream in crystal tower A, the B, this cycle stream rises to the upper end of inner core P always, inside from the upper opening of inner core P along inner core P descends then, so drawn from the bottom of inner core P.

By in partial crystallization tower A, B, forming this cycle stream, so can obtain following effect:

(1) 2 of differing temps kinds of liquid streams have obtained mixing effective, homogeneous.

(2) by preventing the bias current of slip, make the pulp density in the urceolus form homogeneous, the inequality of the residence time of crystalline adduct particle in urceolus is eliminated.

(3) for preventing that the deposition of crystalline adduct particle in urceolus from having obtained to be enough to sufficient linear velocity.

In the present invention, the stock liquid that is made of the phenol solution that contains dihydroxyphenyl propane is added to be circulated in the slip the 1st section partial crystallization tower A, that be cooled by water cooler 6 and goes, so be fed in the 1st section partial crystallization tower.

In addition, in the present invention, the part of the slip of drawing from the bottom of the inner core P of the 1st section partial crystallization tower A is added to and is circulated to the slip the 2nd section partial crystallization tower B, that be cooled by water cooler 26, thereby is supplied in the 2nd section the partial crystallization tower.By the slip that obtains from the 1st section partial crystallization tower A being supplied in such a manner the 2nd section the partial crystallization tower B, so just can obtain following advantage point: the effective cooling of the slip that realization is supplied with; Cooling heat is used in the developmental process of the particle of crystalline adduct; The degree of supersaturation of liquid is alleviated; Make the size distribution of crystalline adduct particle become bigger.

The temperature of phenol solution that contains dihydroxyphenyl propane (from pipeline 1) is than adducts temperature height.Go out 1-20 ℃, the temperature of partial crystallization tower A is 45-70 ℃.Obtain the round-robin slip by pipeline 3, pump 4, water cooler 6 and pipeline 2 and be reduced to below 10 ℃, preferably reduce to below 5 ℃ by water cooler 6.The residence time of phenol solution is 0.5-10 hour among the partial crystallization tower A, is preferably 0.5-5 hour.

On the other hand, be introduced into the slip of micro-crystallization adducts dissolving vessel Q, make 0.5-5 ℃ of temperature rising by well heater 11, thereby be maintained among the micro-crystallization adducts dissolving vessel Q by pipeline 7, pump 8, pipeline 10, well heater 11.Slip residence time in this jar Q is 3-15 minute.

In micro-crystallization dissolving vessel Q, the following crystalline adduct of particle diameter 100 μ m is dissolved, and the slip that micro-crystallization is dissolved is returned to partial crystallization tower A through pipeline 13, thereby promotes crystalline to grow up.

The part of the slip that draw the bottom of the inner core P in the 1st section partial crystallization tower A after pipeline 7, pump 8, pipeline 12 and pipeline 21, is added to be circulated in the slip of partial crystallization tower B by water cooler 26 and goes, so be introduced into the 2nd section partial crystallization tower B.The 2nd section partial crystallization tower B then operates according to the same method shown in the aforementioned partial crystallization tower A.

The temperature of partial crystallization tower B is maintained under 3-10 ℃ the temperature that is lower than partial crystallization tower A.

On the other hand, by the slip of well heater 31, here its temperature has been risen 0.5-5 ℃, and therefore, the temperature that is arranged on the micro-crystallization adducts dissolving vessel Q among the partial crystallization tower B can be maintained under 0.5-5 ℃ the condition that is higher than partial crystallization tower B.

In the micro-crystallization adducts dissolving vessel Q in being arranged on partial crystallization tower B, particle diameter is that the following crystalline adduct of 100 μ m is dissolved, and the slip that micro-crystallization is dissolved is returned to crystal tower B by pipeline 3, thereby has promoted the crystalline growth of crystalline adduct.The concentration of the crystalline adduct the slip that draw the bottom of the inner core P in partial crystallization tower B is below the 35 weight %, be preferably below the 25 weight %, particle diameter is that the containing ratio of the following micro-crystallization adducts particle of 100 μ m is below the 30 weight % in this crystalline adduct, is preferably below the 20 weight %.

The part of the slip that draw the bottom of the inner core P in the 2nd partial crystallization tower B is recovered as the finished product slip by pipeline 35.This slip can be accepted solid-liquid separation as required, the crystalline adduct of gained is sent to the recovery process of dihydroxyphenyl propane, has removed the recovery that has just realized dihydroxyphenyl propane after the phenol.

The finished product slip, as foregoing, can draw from the bottom of the 2nd section inner core P, also can be from micro-crystallization adducts dissolving vessel Q, a part that is circulated to circulation slip partial crystallization tower B, that be heated by pipeline 33 is reclaimed as the finished product slip.

In Fig. 2, shown and used 2 partial crystallization tower A, B to implement the plant system drawing of the inventive method, but, then also can obtain equally implementing if use than this more partial crystallization tower.In other words when using the individual partial crystallization tower of n (n 〉=2) to carry out the partial crystallization operation, be circulated to the 1st section partial crystallization tower, be added into stock liquid in the chilled crystalline adduct slip, thereby be supplied to the 1st section partial crystallization tower, the part of the interior tube bottom crystalline adduct slip of drawing in each the partial crystallization tower from the 1st section to (n-1) section is added into each back one section circulation cooling slip, thereby be sent to each back one section partial crystallization tower, then, the part of the circulation slip that has been heated the partial crystallization tower of the part of the crystalline adduct slip of drawing from the interior tube bottom of the partial crystallization tower of n section (terminal section) or n section is used as the finished product slip and obtains reclaiming.At this moment, the temperature of partial crystallization tower is: make the temperature of the 1st section partial crystallization tower keep the highest, and it is minimum that the partial crystallization tower temperature of n section is remained on, and make till the 1st section beginning to the n section, its temperature is reduced one by one.Temperature head between each partial crystallization tower and the partial crystallization tower that each is back one section is 3-10 ℃, is preferably 5-8 ℃, and the temperature of each back one section partial crystallization tower also only keeps this temperature head.

According to the 2nd process of the present invention, can be with the good dihydroxyphenyl propane of higher yield acquisition purity height, form and aspect, the crystalline adduct of phenol.

The crystalline adduct of this dihydroxyphenyl propane phenol can be removed these phenol by separation, and provides purity height, dihydroxyphenyl propane that form and aspect are good.

(the 3rd process)

Then by figure, for describing for the 3rd process that obtains crystalline adduct.

Fig. 3 is the plant system drawing for the 3rd process of implementing the present invention.In the figure, 1 is that pump, A are the partial crystallization tower for well heater, 6,7 for water cooler, 5 for the dissolving vessel of micro-crystallization adducts, 4 for inner core, 3 for urceolus, 2.

Partial crystallization tower A has 2 weight structures, because it has inserted the inner core 2 that its top is provided with opening portion in the urceolus 1 of closed structure.

The said closed structure of the present invention is not meant that the partial crystallization tower is in the atmosphere opening state, and is meant with rare gas element and is sealed.

If be in atmosphere opening, then will absorb the part of oxygen in the atmosphere in the slip in the partial crystallization tower, thereby the form and aspect of adducts are worsened, meanwhile more seriously, also can handle to back segment and bring detrimentally affect, this just can't obtain high-quality adducts and dihydroxyphenyl propane.Therefore in the partial crystallization tower,, be necessary to seal with rare gas element in order to prevent sneaking into of oxygen.If at this moment can prevent sneaking into of oxygen, that just not necessarily needs high voltage bearing airtight pressure vessel.In addition, this partial crystallization tower, be not direct fairlead partly to be set at urceolus, but on the axle inner core is being set among the slip cycle stream of inside, make the cycle stream of this slip rise to top, make slip produce overflow from the opening portion on inner core top, and make it to descend, so draw from interior tube bottom along inner core is inner.By this step, can do the mixing of homogeneous to the circulation slip of introducing, and can guarantee the fully left alone without help time of staying for the adducts particle.

To implement the present invention effectively, at first be the phenol solution that will make the dihydroxyphenyl propane that contains processed raw material by pipeline 8 and pipeline 9 and then be fills up in the partial crystallization tower A, draw phenol solution from the bottom of inner core 2 by pipeline 10 simultaneously, make it to be circulated to continuously in the urceolus of partial crystallization tower A bottom by pipeline 11, pump 6, pipeline 12, water cooler 4, pipeline 13 and pipeline 9.By this operation, the phenol solution in the partial crystallization tower A is cooled, and has separated out crystalline adduct, has generated the slip that contains crystalline adduct.Then, this slip is drawn,, be circulated to again in the urceolus 1 of partial crystallization tower A bottom after in water cooler 4, being cooled according to foregoing such from the bottom of inner core 2.

In addition, the bottom from inner core 2 makes the part of slip be circulated to the inside of the urceolus 1 of partial crystallization tower A bottom continuously by pipeline 10, pipeline 14, pump 7, pipeline 15, well heater 5, jar 3 and pipeline 16,17.By this operation, the micro-crystallization adducts particle from the derivative slip in the bottom of inner core 2 is dissolved in jar 3, and the low slip of micro-crystallization adducts particle containing ratio is circulated to the inside of partial crystallization tower A.The containing ratio of the micro-crystallization adducts particle in its result, partial crystallization tower A has obtained minimizing.

Then, under such state, make stock liquid pass through pipeline 8, and pipeline 9 introduce in the urceolus 1 of partial crystallization tower A bottom, draw the finished product slip from the bottom of inner core 2 by pipeline 20 simultaneously.

At this moment, in that being flowed to run by gravity under the situation of later process, this slip drawn by pipeline 20.Situation if not so then can be drawn wherein a part from the discharging pipeline 21 of pump 7.In addition, also can reclaim, make it crystalline adduct slip as finished product by the few a part of slip of 18 pairs of micro-crystallization containing ratios of pipeline.

In the present invention, the slip that the slip that the temperature by pipeline 9 has descended and the temperature by pipeline 16,17 have risen in being introduced into urceolus 1 in, be introduced in the urceolus from the urceolus bottom according to the mode that produces same direction cycle stream.At this moment, preferably introduce, and the position of introducing should be inequality according to the direction that forms tangent line with the urceolus inner peripheral surface.The position of introducing is too near, can produce partial mobile confusion, thereby can not get slyness cycle smoothly stream, in addition, considers from the structure and the intensity thereof of partial crystallization tower that this also is worthless.So the introducing position of these 2 kinds of slips is to represent with the angle of distance urceolus central point, preferably operate the position that has separated like this with the 90-180 degree.Moreover, because be to have produced unidirectional cycle stream, so the introducing position of 2 kinds of slips is maintained at the same horizontal plane, be bottom at least, even there is a difference of height also unimportant at urceolus.

As previously mentioned, the part of the slurry of getting the raw materials ready by pipeline 9 and pipeline 16,17, be introduced in the urceolus according to the mode that forms same direction cycle stream, simultaneously, this cycle stream rises to the upper end of inner core 2 in urceolus 1, upper opening from inner core 2 descends along inner core 2 then, is drawn by pump 10 from the bottom of this inner core.

By in urceolus 1, producing such cycle stream, can obtain following effect.

(1) can make 2 kinds of different liquid streams of temperature obtain effectively and uniformly to mix.

(2) can prevent the bias current of slip, because can make the interior pulp density of urceolus reach evenly, so can eliminate crystalline adduct particle inequality on the residence time in urceolus.

(3) can obtain sufficient linear velocity, this speed is enough to prevent the deposition of crystalline adduct particle in urceolus.

In addition, as previously mentioned, the part of the slip of drawing from inner core 2 bottoms is by pipeline 10, pipeline 14, pump 7, well heater 5, jar 3 and pipeline 16,17 when being circulated to partial crystallization tower A, micro-crystallization adducts in the slip in jar 3 with regard to dissolved disappearance, the slip that contains the thick crystalline adduct of determining size is by pipeline 16,17 are circulated to partial crystallization tower A, so, the particle diameter of contained crystalline adduct is by unification in the partial crystallization tower A, and it is low just to have generated micro-crystallization adducts particle containing ratio in prilling tower A, the high crystalline adduct of thick crystalline adduct particle containing ratio.Micro-crystallization adducts among the partial crystallization tower A is because its surface-area is bigger, so the material that constitutes coloration reason has been shown very high adsorptivity.Therefore, by the micro-crystallization adducts particle in the crystalline adduct that is obtained among the partial crystallization tower A is done to reduce as much as possible, just can obtain the good crystalline adduct of form and aspect.According to present inventors' research, particle diameter should be preferably in below the 20 weight % below 30 weight % at the micro-crystallization particle containing ratio below the 100 μ m in the crystalline adduct, so just can obtain the high crystalline adduct of the good purity of form and aspect.

Contain from the temperature of the phenol solution of the dihydroxyphenyl propane of pipeline 8 and exceed 1-20 ℃ than the temperature of saturation of adducts, the temperature of partial crystallization tower A is 45-70 ℃.The slip that is recycled by pipeline 11, pump 6, water cooler 4 and pipeline 9 is cooled in water cooler 4 below 10 ℃, preferably below 5 ℃.The residence time of phenol solution in partial crystallization tower A is 0.5-10 hour, is preferably 0.5-5 hour.

On the other hand, be introduced into the slip of micro-crystallization adducts dissolving vessel 3, make 0.5-5 ℃ of temperature rising, be maintained at then in the micro-crystallization dissolving vessel 3 by well heater 5 by pipeline 14, pump 7, pipeline 15, well heater 5.The residence time of phenol solution in this dissolving vessel 3 is 3-15 minute.

In micro-crystallization dissolving vessel 3, the crystalline adduct below the particle diameter 100 μ m is dissolved, and in the crystalline adduct in the slip of pipeline 16, particle diameter is below the 30 weight % at the crystalline adduct particle containing ratio below the 100 μ m, is preferably in below the 20 weight %.

The part of the slip of drawing from the bottom of interior tower 2 is recovered as the finished product slip by pipeline 2.At this moment, adopt run by gravity to make this pulp flow is to adopt pipeline 20 during one section operation backward.If not so, then also can draw a part wherein from the discharge nozzle 21 of pump 7.In addition, also can reclaim by the part of the few slip of 8 pairs of micro-crystallization containing ratios of pipeline, thereby as the crystalline adduct slip of finished product.Then, again this slip is implemented and aforementioned same partial crystallization processing.In addition, handle by this slip being made solid-liquid separation, thereby can obtain crystalline adduct.

According to the 3rd process of the present invention, can generate the containing ratio crystalline adduct low, that form and aspect are good of micro-crystallization adducts particle with higher efficient, this crystalline adduct just can provide the good dihydroxyphenyl propane of a kind of form and aspect after phenol has been removed in separation.

(the 4th process)

Then, according to Fig. 4, for being illustrated for the 4th process that obtains crystalline adduct of the present invention and for the partial crystallization device of realizing this process.

In this Fig. 4, A is the 1st partial crystallization tower, and B is the 2nd partial crystallization tower, and 3-4 is the 1st water cooler commonly used, and 5 is standby water cooler, and 6-7 is the 2nd water cooler commonly used.

Phenol solution as the dihydroxyphenyl propane of raw material is at first introduced the 1st partial crystallization tower A from pipeline 101.The part of the 102 crystalline adduct slips of drawing is sent to the 2nd partial crystallization tower B through pump 8 and pipeline 104 by the road from the bottom of the 1st partial crystallization tower A, and a part is returned to the 1st partial crystallization tower from pipeline 103 through pump 9 and 10 and water cooler 3 again after cooling.Temperature in the 1st partial crystallization tower determine by following factor: the temperature of the stock liquid that flows into from pipeline 101 and temperature and their inflow ratio thereof from the circulation fluid of pipeline 103 inflows.The equimolar crystalline adduct of dihydroxyphenyl propane and phenol to precipitate into always with the corresponding concentration of this temperature till, so, from pipeline 102 begin through pump 9 and 10 and water cooler 3 and 4 to arrive the liquid that is flowing the circulation line of pipelines 103 be the slip that contains above-mentioned crystalline adduct.Equally, the part of 105 derivative liquid 107 is sent to reclaiming the filtration units of crystalline adduct by the road by the road from the bottom of the 2nd partial crystallization tower B, a part then through pump 12 and 13 and water cooler 6 and 7 accept cooling, returned to the 2nd partial crystallization tower B from pipeline 106 then.Temperature in the 2nd partial crystallization tower B determine by following factor: the temperature of fluid temperature that flows into from pipeline 104 and the liquid that flows into from pipeline 106 and flowing into compares.Dihydroxyphenyl propane and phenol etc. the mole crystalline adduct to precipitate into always with the corresponding concentration of this temperature till.

So, from pipeline 105 through pumps 12 and 13 and water cooler 6 and 7 to arrive the liquid that is flowing the circulation line of pipelines 106 be the slip that contains above-mentioned crystalline adduct.

The pipeline that has comprised pump 11 and water cooler 5 is the spare duct that can shift its load when other pump and water cooler thereof when pipeline is pulled down.Water cooler 3,4 commonly used,, 6 and and the utilization table look-up of standby water cooler 5 as shown in the following Table 1.

(table 1)

Operation mode	1	2	3	4	5
						Water cooler 3	A	/	A	A	A
Water cooler 4	A	A	A	/	A
						Water cooler
5	/	A	B	A	B
						Water cooler 6	B	B	/	B	B
Water cooler 7	B	B	B	B	/

In table 1, A represents the slip of the 1st partial crystallization system is cooled off, and B represents the slip of the 2nd partial crystallization system is cooled off.Operation mode is moved in turn from 1 to 5, just finished the 1st circulation when returning 1.In order to dissolve, need about 1 hour after more than the fluid temperature in the water cooler rises to the crystallization solvent temperature to separating out in the crystalline adduct of heat-transfer surface.Because of can causing heat-transfer effect to descend adhering to of crystalline adduct, the time that can keep till need to regenerate is then depended on working conditions, but also is tens hours at least, so above-mentioned circulation just can easily be finished.The 4th process of the present invention and for implementing the partial crystallization device of this process, as previously described, it has following feature: the partial crystallization device (using water cooler that the slip of crystalline adduct is cooled off) by the exterior cooling formula is operated, a plurality of water coolers are set, make one of them as standby water cooler, with the water cooler beyond the standby water cooler crystalline adduct slip is cooled off, separate out crystalline on the heat-transfer surface, its heat transfer efficiency is low water cooler and standby water cooler exchange, thereby realization continuous operation, just can dissolve by the water cooler that heat transfer efficiency the descended operation back of heating simultaneously, thereby obtain regenerating attached to the crystalline adduct on the heat-transfer surface.At this moment, it is also passable that one in a plurality of water coolers is fixed up as standby water cooler all the time, perhaps recycles each water cooler also passable in turn as standby water cooler.

The partial crystallization tower can be 1 in the present invention, but preferably as shown in Figure 4, carries out 2 sections partial crystallizations thereby the partial crystallization tower is provided with by 2 towers polyphone, and water cooler commonly used individually is arranged on each partial crystallization tower, yet each is shared one of two partial crystallization towers with water cooler.The partial crystallization tower is arranged in series with 2 towers carries out 2 sections partial crystallizations, because the temperature difference of temperature can be dwindled in the inflow temperature of the crystalline adduct slip of each tower and the tower, thus can avoid crystalline sharply to separate out, so can obtain the high big crystalline adduct of purity.In addition, because the load of water cooler is descended, separate out so can suppress crystalline at the heat-transfer surface of water cooler.Then, be that two towers are shared if make standby water cooler, then can reduce the cost of equipment.At this moment, being cooled to of 2 kinds of liquid that the temperature of standby water cooler and solute concentration are inequality alternately carried out, if heat-exchange capacity is identical, temperature and solute concentration are more or less different, also can not cause what problem.

Using water cooler the crystalline adduct slip to be carried out in the refrigerative exterior cooling formula partial crystallization device, the liquid that flows through in the water cooler is generally the slip that contains crystallization (crystalline adduct of dihydroxyphenyl propane and phenol), water cooler is a kind of indirect heat exchanger, slip by water cooler is cooled off through heat-transfer surface, so just separated out and corresponding this part crystallization of this temperature decline.Yet, between the reduction of temperature and crystalline are separated out, a temporal hysteresis is arranged, wait a little just has crystallization to separate out after reaching hypersaturated state at leisure.In addition, separate out crystallization, the existence of kind of crystalline substance must be arranged, usually, the crystallization in the slip is being waved this effect as kind of a trichite, be new crystallization generation, it would be better to say that it is to have separated out crystallization because of the growth of the crystallization in the slip Already in.Therefore, attached to the thing dirt (being made of fine crystalline and impurity) of the heat-transfer surface of water cooler, formation speed originally is also less big, but once adhering to, this just works as kind of crystalline substance so, so this speed is just constantly accelerated.Along with the accumulation of this thing dirt, at first be to have produced the problem that heat transfer efficiency (being cooling efficiency) falls greatly, in addition, along with peeling off of thing dirt, the purity that is sent to the product of partial crystallization tower also can descend.So normally, if the thing dirt accumulates, should pull down water cooler so and clean.In the time that this operation is carried out, because having to make the partial crystallization operation stops, so just to a certain extent, the operation of successive partial crystallization just has to often stop, and the result just causes such a case: this water cooler can only use till the thing dirt accumulation of a great deal of.

According to the present invention, foregoing problems is all solved.In the present invention, at first be not to remove the thing dirt, but just change water cooler (the refrigerative load transfer to standby water cooler) when on the water cooler heat-transfer surface, only separating out a spot of crystallization.For this water cooler of having pulled down can not be to add heat-eliminating medium as required, but washes with the medium of heating, so can remove the fine crystalline of separating out on heat-transfer surface through dissolving.This medium of heating, owing to be to be provided with circulation line in addition, as long as this water cooler is connected on the circulation line of the medium of heating.Because fine crystallization is to be removed before forming hard thing dirt,, only merely this water cooler is pulled down to heat from pipeline and can avoid the problem of above-mentioned dirt settling dirt even do not carry out the operation that the sort ofization is time-consuming and manpower cleans the thing dirt.

(the 5th process)

Below, by the reference drawing, for describing for the 5th process that obtains crystalline adduct.

Fig. 5 has represented an example for the flow process of implementing the inventive method.In Fig. 5 A-1, A-2, A-3, represent the 1st partial crystallization operation, the 2nd partial crystallization operation, the 3rd partial crystallization operation respectively.B-1, B-2, B-3 represent the 1st solid-liquid separation process, the 2nd solid-liquid separation process, the 3rd solid-liquid separation process respectively.C-1, C-2 represent the 1st dissolution process, the 2nd dissolution process more again of crystalline adduct respectively.

When making crystalline adduct, in the flow process of steady state, contain the phenol solution of handling with the dihydroxyphenyl propane of stock liquid as partial crystallization and be introduced into the 1st partial crystallization operation A-1 by pipeline 1 according to flow process shown in Figure 5.

The partial crystallization resultant that obtains among the 1st partial crystallization operation A-1 is introduced among the 1st solid-liquid separation process B-1 by pipeline 2, here, the 1st crystalline adduct D-1 and the 1st mother liquor F-1 are separated, the 1st mother liquor F-1 is because contain useful compositions such as phenol, dihydroxyphenyl propane, so after having done suitable processing, just be circulated in the reaction process of phenol and ketone.The 1st crystalline adduct of from the 1st partial crystallization resultant, separating, the 2nd mother liquor F-2 that obtains among the 2nd solid-liquid separation process B-2 with back segment cleans, and the 1st cleaning discharge opeing E-1 that obtains in this cleaning is circulated in the reaction process of phenol and acetone again.

As previously mentioned, the 1st crystalline adduct D-1 that has done to clean with the 2nd mother liquor F-2 is introduced into the 1st dissolution process C-1 again, after making dissolution process with the scavenging solution E-2 (from the 2nd solid-liquid separation process B-2 of back segment) of the 2nd crystalline adduct, be imported into the 2nd partial crystallization operation A-2 by pipeline 3 again.

The partial crystallization resultant that obtains in the 2nd partial crystallization operation A-2 is introduced into the 2nd solid-liquid separation process B-2 by pipeline 4, be separated into the 2nd crystalline adduct D-2 and the 2nd mother liquor F-2 here, the 2nd mother liquor F-2 foregoingly is used to clean crystalline adduct D-1 (separating) like that from the 1st solid-liquid separation process B-1.On the other hand, the 2nd crystalline adduct D-2 is that the 3rd mother liquor that obtains among the 3rd solid-liquid separation process B-3 with back segment is done to clean, and the 2nd cleans discharge opeing as previously mentioned, is that the dissolving as the 1st crystalline adduct D-1 is used with phenol solution.

As previously mentioned, the 2nd crystalline adduct D-2 that has cleaned with the 3rd mother liquor F-3 is introduced into the 2nd dissolution process C-2 again, cleaning discharge opeing E-3 (from the 3rd solid-liquid separation process B-3 of back segment) with the 3rd crystalline adduct does to be imported into the 3rd partial crystallization operation A-3 by pipeline 5 again after the dissolution process.

The partial crystallization resultant that obtains in the 3rd partial crystallization operation A-3 is introduced into the 3rd solid-liquid separation process B-3 by pipeline 6, be separated into the 3rd crystalline adduct D-3 and the 3rd mother liquor F-3 here, the 3rd mother liquor F-3 is used to clean the 2nd crystalline adduct D-2 (being separated) as previously mentioned in the 2nd solid-liquid separation process B-2.

The 3rd crystalline adduct D-3 cleans with refining phenol F, and the 3rd cleaning discharge opeing E-3 is used as the 2nd dissolving phenol solution of the 2nd crystalline adduct among the dissolution process C-2 more as previously mentioned.

The 3rd crystalline adduct D-3 that has cleaned with the refining phenol F of gained in the 3rd solid-liquid separation process is taken as finished product and reclaims.

In the present invention, as refining phenol normally,, so just not limited by what as long as it dissolves look APHA below 15.

The refining phenol that is suitable for using in the present invention has, for example, and the refining thing of shown various phenol in the process for purification of above-mentioned crystalline adduct.

In the present invention, as the scavenging solution of each section crystalline adduct, in its part, use back one section mother liquor at least, at this moment can be as required, simultaneously and with the part of each one section cleaning.In addition, as the back segment phenol solution of the dissolving of the crystalline adduct in dissolution process usefulness again, at least in its part available on from the cleaning discharge opeing of back segment, at this moment can be as required simultaneously and use a part from the mother liquor of back segment.In the present invention, be used for scavenging solution that crystalline adduct cleans and be the phenol solution of this crystalline adduct of dissolving, contained impurity concentration in the two is along with flowing to later process, that is: when the 1st section partial crystallization operation flowed to the partial crystallization operation of n section, impurity concentration will diminish.In other words, the impurity concentration in each section in the phenol solution of the scavenging solution of employed crystalline adduct and crystalline adduct dissolving usefulness all is that the last period is than back one section high.Impurity concentration in each adjacent section in the employed scavenging solution becomes geometric progression ground to reduce basically.

Yet the impurity of indication is meant the by product that is occurred when generating dihydroxyphenyl propane in the reaction of phenol and acetone in this specification sheets.This class impurity comprises metamer, chroman compound of dihydroxyphenyl propane etc.

Moreover, in the present invention,, can omit from the 1st section part to each matting of n-1 section according to the purity requirement of product adducts, also can intactly deliver to dissolution process again to resulting crystalline adduct in the solid-liquid separation process.This moment again in the dissolution process employed phenol solution be resulting mother liquor in the back segment solid-liquid separation process (or cleaning discharge opeing).

Like this, in the present invention,, by employed cleaning in each section is adjusted with the amount of phenol solution, just can reduce the usage quantity of phenol on the whole, so just might reduce cost according to the purity requirement of product adducts.

Partial crystallization operation of the present invention has more than 2 sections, has shown the example that comprises 3 sections partial crystallization operations among the figure, even but the partial crystallization operation more than 4 sections, also can be according to being implemented with the same method in front.

According to the 5th process of the present invention, only in the cleaning of the crystalline adduct of terminal section, use refining phenol, just can obtain high-grade crystalline adduct.So in the present invention, the usage quantity of the refining phenol of high purity only needs to get final product on a small quantity, the manufacturing cost of crystalline adduct has also obtained reduction.

(the 6th process)

Below will illustrate for obtaining the 6th process of crystalline adduct of the present invention.

The crystalline adduct slip that is used as the raw material of this process has: the resultant of reaction of phenol and ketone is done that partial crystallization is handled and the crystalline adduct slip that obtains; Make the crystalline adduct slip that obtains after dissolving again and the partial crystallization processing to separating from the crystalline adduct of this slip.

In the present invention, this crystalline adduct slip is made filtration treatment and then from mother liquor the fractional crystallization adducts time, in slip in the contained crystalline adduct, the at least a portion that makes the micro-crystallization adducts composition of particle diameter below 100 μ m is towards filtrate (mother liquor) side shifting, so to obtain particle diameter be the following micro-crystallization adducts of the 100 μ m ratio that becomes branch below the 20 weight %, the thick crystalline adduct below the 15 weight % preferably.At this moment in order to make micro-crystallization adducts composition, can realize by selected and the selecting of filter operation condition of filtering material towards filtered liquid one side shifting.As filtering material generally is 100-150 μ m, the material of 100-125 μ m preferably.In addition,, make micro-crystallization adducts composition in filtrate one side shifting, can come implementation and operation according to the thickness of the piece thing of the resulting crystalline adduct of this filtration treatment and to the number of times that this block itself carries out back washing according to filtration condition.

In the present invention, according to aforementioned resulting thick crystalline adduct, the foreign matter content of itself is low and of high grade, if further this thick crystalline adduct is cleaned with refining phenol, then can obtain higher grade again.At this moment, the refining thing of related various phenol in the process for purification that can use aforementioned crystalline adduct as refining phenol.

Cleaning with refining phenol is done crystalline adduct can realize by such way: make crystalline adduct reach sufficient with refining phenol and contact.This clean for example can be carried out in for the equipment for separating liquid from solid of isolating the filter of crystalline adduct and separating centrifuge etc., removes mother liquor from crystalline adduct, then, refining phenol is introduced in this equipment for separating liquid from solid clean.Also can in other steel basin, clean to row from crystalline adduct equipment for separating liquid from solid, that have a small amount of mother liquor to adhere to refining phenol.Usage ratio for the refining phenol of crystalline adduct is such: be more than 50 weight unit during crystalline adduct 100 weight unit, be preferably more than 100 weight unit.

By made the crystalline adduct of clean with above-mentioned refining phenol, its surface attachment has refining phenol, but this product is sent to the operation of removing of phenol again, has here removed after the phenol, just can reclaim highly purified finished product dihydroxyphenyl propane.Remove phenol from crystalline adduct, can carry out as methods such as distillation, extraction, steam desorbs with being people's known method.

It is good easily to obtain form and aspect according to the present invention, is not easy crystalline adduct painted, good thermal stability.In addition, from this crystalline adduct, remove after the phenol and the dihydroxyphenyl propane that obtains also to be form and aspect good, be not easy painted higher-grade material.

Below, will be for being described in detail for each process that obtains dihydroxyphenyl propane.

In the present invention, as crystalline adduct, can use to be in neutrallty condition in fact, and dissolve look APHA below 15, be preferably in the material below 5.

In reaction, as the strong acid type material of the strong ion exchange resin that hydrochloric acid, sulfuric acid, sulfone acid type are arranged of acid catalyst etc. for the phenol that obtains dihydroxyphenyl propane and acetone.Such strongly-acid material in the reactive system of phenol and acetone, except as the catalyzer, also can demonstrate the generation that can impel coloring material and impurity under the condition of heating, thereby feasible dihydroxyphenyl propane and the form and aspect of phenol and the decline of purity that is recovered.Therefore strongly-acid material like this in order to be unlikely to flow out to the follow-up phenol removal process of following heating condition, just to have proposed one and has removed after reaction or the neutral scheme.People also propose such scheme, and for example, when reacting as catalyzer with hydrochloric acid, after the reaction, by resultant being added heat extraction hydrochloric acid, residual hydrochloric acid neutralizes with alkali, be neutralized to pH5-6 till (special public) according to 47-43937.In addition, in with the strong acid ion exchange resin reaction, organic sulfoxide acid is broken away from, owing to be to have sneaked in the resultant, so available weak-base ion-exchange resin is to this organic sulfoxide acid neutralize (No. 4191843, United States Patent (USP)).On the other hand, the form and aspect of phenol and dihydroxyphenyl propane and purity are not only because acid also can be owing to alkali causes lowly, and the neutralization of being undertaken by the alkali of strong acid type material must be no more than the point of neutralization.

More than, in the presence of the strongly-acid material, phenol and acetone are reacted, the strongly-acid material that exists in the resultant of reaction after reaction, should neutralize being no more than under the situation of the point of neutralization, perhaps it is removed from reactive system.In addition, used alkali still has when remaining in the N-process of strongly-acid material, and that just must also be removed these alkali, in addition, removing of strongly-acid material that exists in the resultant of reaction or alkali can be removed by using multistage partial crystallization operation in follow-up partial crystallization operation.

Acted among the present invention, be in crystalline adduct under the neutrallty condition in fact, the crystalline adduct that the influence that is meant aforesaid strongly-acid material and alkaline matter has been removed.Such crystalline adduct is added and is dissolved in its acidity adjusted is that pH should be 4.90-5.50 when measuring with the pH measuring method under the condition of unionized in fact of phenol, is preferably 4.95-5.20 in 0.5 the methanol aqueous solution to pH.Yet the pH of shown crystalline adduct in this specification sheets measures according to aforementioned measuring method.

In the present invention, as crystalline adduct, as previously mentioned, be to adopt the material that is in neutrallty condition in fact, at this moment, crystalline adduct dissolve look APHA to remain on below 15 to well.Dissolve the following crystalline adduct of look APHA15 as previously described, can get off to obtain, in case of necessity, can obtain by the partial crystallization hop count that increases the partial crystallization operation by making crystalline adduct remain on substantial neutrallty condition.In addition, also can obtain by adopting refining phenol to come that crystalline adduct is done cleaning.

Under the occasion of crystalline adduct being done to clean with refining phenol, as this refining phenol can be any this class phenol coloration reason, that the impurity containing ratio is few that does not constitute the product dihydroxyphenyl propane.In the present invention, as this refining phenol, make usually to dissolve look APHA below 10, be preferably in below 5.

As the refining phenol that is suitable for using among the present invention, for example can list various refining phenol related in the process for purification of aforementioned crystalline adduct.

The cleaning of the crystalline adduct that the refining phenol of employing carries out can be used to make crystalline adduct and refining phenol make the method that fully contacts.This clean for example can be carried out in for the equipment for separating liquid from solid that makes isolating filter of crystalline adduct and separating centrifuge etc., earlier mother liquor is removed from crystalline adduct, refining phenol is introduced in this equipment for separating liquid from solid cleaned then.Also can in other steel basin, adopt refining phenol that row is cleaned from crystalline adduct equipment for separating liquid from solid, that adhered to a small amount of mother liquor.Usage ratio for the refining phenol of crystalline adduct is: the crystalline adduct of 100 weight unit is the 30-1000 weight unit, is preferably the 100-300 weight unit.The refining phenol that has used in the clean process of crystalline adduct can be intactly, or after the cleaning that is used for rough crystalline adduct (leading portion partial crystallization engineering is resulting), as the raw material phenol of the building-up reactions operation of dihydroxyphenyl propane and be recovered.

The temperature that crystalline adduct is heated when dissolving is 115-180 ℃, is preferably 120-150 ℃, and in addition, pressure is absolute pressure 1.0-5atm, is preferably 1.0-1.9atm, and the heating of crystalline adduct dissolves, and can use the heating container of heating-type to carry out.

Remove phenol through evaporation from the crystallization melt, can pass through distillation tower, thin-film evaporator carries out.At this moment, evaporation unit can be a multistage, but final Heating temperature is 160-200 ℃, is preferably 170-185 ℃, and pressure is to adopt reduced pressure, is generally 100 holders, is preferably the 5-40 holder.

The comparatively ideal evaporation of this phenol is removed, and is to heat up in a steamer most phenol with thin-film evaporator, and residual micro-phenol is removed with the steam desorb.At this moment, the feed rate of steam is: the ratio to dihydroxyphenyl propane is the 1/50-1/5 of weight ratio, is preferably 1/25-1/10.

The product dihydroxyphenyl propane that obtains as stated above, its purity are more than 99.95 weight %, and form and aspect also are excellent, have the following form and aspect of APHA20 usually.This high-grade dihydroxyphenyl propane is well suited for as the raw material dihydroxyphenyl propane of high brilliant position polycarbonate and Resins, epoxy, moreover, be used for the optical field dihydroxyphenyl propane and also be well suited for.

(the 2nd process)

Below, will illustrate for obtaining the 2nd process of dihydroxyphenyl propane of the present invention.

Employed evaporation process raw material among the present invention is to contain that to dissolve look APHA be the crystalline adduct (being in neutrallty condition in fact) below 15 and the mixture of aliphatic carbonic acid.

In order to implement the present invention effectively, be in crystalline adduct or the mixture of its melt or this crystalline adduct and phenol or its melt of neutrallty condition in fact, in the presence of aliphatic carbonic acid, dissolved, under reduced pressure be heated, removed phenol through evaporation.

Aliphatic carbonic acid used in the present invention when the dihydroxyphenyl propane that makes the state of dissolving and air are made Long contact time and make it keep pyritous, can demonstrate the effect that prevents that dihydroxyphenyl propane is painted.In the present invention, accept evaporation process,, just obtained good and the dihydroxyphenyl propane that can be not painted of form and aspect by the phenol in the crystalline adduct is removed by being in the mixture that crystalline adduct under the neutrallty condition and aliphatic carbonic acid constitute in fact.

As aliphatic carbonic acid, preventing painted effect if can demonstrate to dihydroxyphenyl propane, its kind is just unrestricted so, can adopt to be the known material of people.As having of this class material, for example formic acid, oxalic acid, citric acid, tartrate, glycol acid, lactic acid, oxysuccinic acid, glycerol acid etc.These materials when the temperature more than 160 ℃, can take place to decompose or the opposite sexization in reaction process, have shown and can play the painted agent that prevents to dihydroxyphenyl propane.

In the present invention, prevent agent as painted, must use aliphatic carbonic acid, if use barkite, terephthalic acid, sodium phosphate etc. so just to can not get the effect of sufficient that prevents that dihydroxyphenyl propane is painted, make Long contact time if at this moment make dihydroxyphenyl propane and air, and when remaining on high temperature, so will be painted in dihydroxyphenyl propane, thereby make the remarkable variation of form and aspect.The addition of aliphatic carbonic acid for crystalline adduct, is the 1-100 ppm by weight, preferably the 5-50 ppm by weight.

In addition, in the present invention, in the presence of oxalic acid or citric acid, crystalline adduct or the mixture that contains this adducts are heated when dissolving, this dissolves temperature is 115-180 ℃, be preferably 120-150 ℃, dissolving pressure is 1-5atm, is preferably 1.0-1.9atm.The air conditions that dissolves is, the alap air conditions of oxygen concentration, and usually, concentration of oxygen is below the 0.005vol%, to be preferably below the 0.001vol%.

In addition, among the present invention, for the mixture that makes crystalline compounds at short notice or contain this crystalline compounds is dissolved, should be to use that top said to resemble refining phenol such, almost non-staining hot phenol dilutes and dissolves, and also can dissolve in crystalline adduct or the dissolving in the liquid that is through with of mixture of containing this adducts.

In the present invention, make evaporation process to the heating melt that obtains through aforesaid method, evaporation process at this moment be 130-200 ℃ and the decompression condition.More desirable evaporation process be temperature in melt integral body below 185 ℃, and at least a portion of melt is carried out when accepting heating under the temperature more than 160 ℃.If the temperature of evaporation process is too low, then just can not give full play of as the effect of the painted aliphatic carbonic acid that prevents agent and add, on the other hand,, then can cause the painted decomposition of aliphatic carbonic acid if this temperature is too high.This evaporation process is under reduced pressure carried out, and this pressure is below 100 holders, is preferably the scope (this paper said " holder " all refers to mmHg) of 5-40 holder.In addition, the air conditions of evaporation process is the alap condition of oxygen concentration, and usually, oxygen concentration is below the 0.005vol%, to be preferably below the 0.001vol%.

Just can obtain the high form and aspect of purity according to the present invention excellent and can prevent painted finished product dihydroxyphenyl propane when dissolving.In addition, the storage stability of this material is also good.

(the 3rd process)

Below, will illustrate for obtaining the 3rd process of dihydroxyphenyl propane of the present invention.

The crystalline adduct of employed dihydroxyphenyl propane and phenol among the present invention can be made with known method.That is: can in the presence of strong acid catalyst, excessive phenol and acetone be reacted, obtain containing after the resultant of reaction of dihydroxyphenyl propane, again this resultant of reaction be made partial crystallization and handle, so just can obtain the crystalline adduct of dihydroxyphenyl propane and phenol.At this moment, the purity of crystalline adduct can obtain to improve by multistage partial crystallization operation or by the method that crystalline adduct is done to clean, but in crystalline adduct, also might sneak into strongly-acid material (in the reaction of phenol and ketone as catalyzer and used).This strongly-acid material can react with phenol and dihydroxyphenyl propane, thereby can cause the formation of coloring material and impurity under heating condition, so the purity of just feasible phenol that is recovered and dihydroxyphenyl propane descends.On the other hand, the strongly-acid material that was used as catalyzer when the reaction of phenol and acetone is reacting after neutralizing treatment generally all is removed.Also can be removed by multistage partial crystallization operation.But such removing usually is not too thorough, usually sneaks into the acidic substance of trace in the crystalline adduct.

In the present invention, be that the crystalline adduct that contains this micro-strong acid is used as raw material.The mixed volume of the strongly-acid material among the present invention in the employed crystalline adduct is generally 0.3meq/l.Such crystalline adduct interpolation is dissolved in the methanol aqueous solution that the acidity adjusted is pH5.0, should records pH4.0-5.5, be preferably pH4.3-5.2 with the pH assay method under the condition of unionized in fact of phenol.The crystalline adduct meaning in this specification sheets under the said solutions of weak acidity refers to the crystalline adduct of above-mentioned PH scope.

In the present invention, as crystalline adduct, as previously mentioned, be to use the material that is under the acidic conditions, at this moment, the look APHA that dissolves of crystalline adduct is remained on below 15.Dissolve the following crystalline adduct of look APHA15, can obtain, in addition, can obtain by crystalline adduct being cleaned with refining phenol by in the partial crystallization operation of partial crystallization crystalline adduct, increasing the partial crystallization hop count.

In order to implement the present invention effectively, can in the presence of aliphatic carbonate, dissolve processing to the crystalline adduct that is in solutions of weak acidity, under reduced pressure heat, remove phenol through evaporation.

Employed aliphatic carbonate among the present invention can react with the strongly-acid material of the trace of being sneaked in the crystalline adduct, thereby this is neutralized, but this neutralization reaction has also produced free aliphatic carbonic acid as by product simultaneously.So, in the present invention, in the presence of aliphatic carbonate to crystalline adduct dissolve with evaporation process in do not exist owing to react the strongly-acid material that the back generates coloring material and impurity, so just can obtain the dihydroxyphenyl propane of form and aspect excellence with phenol and dihydroxyphenyl propane.Moreover the free carbonic acid that produces as by product has and prevents painted effect, so the dihydroxyphenyl propane that is obtained, the painted situation of its melt has just significantly been restrained.

As aliphatic carbonate, can be any this class material that obtains behind the strongly-acid substance reaction, an alkali metal salt, ammonium salt, alkali earth metal salt are generally arranged.In addition, as the aliphatic carbonic acid composition of aliphatic carbonate, can use and to demonstrate the painted material that prevents effect to dihydroxyphenyl propane, have for the known material of people: formic acid, oxalic acid, citric acid, tartrate, glycol acid, lactic acid, oxysuccinic acid, glycerol acid etc.This class aliphatic carbonate when the temperature more than 160 ℃, can cause and decompose or the opposite sexization, but can play the painted effect that prevents agent to dihydroxyphenyl propane in reaction process.The addition of aliphatic carbonate is to make crystalline adduct neutral amount in fact fully, just the strongly-acid material in and a great deal of.The interpolation of carbonate surpasses in this and a great deal of is worthless, and the excessive existence of carbonate can make the form and aspect variation of product dihydroxyphenyl propane.In addition, when adding carbonate, the amount of secondary free carbonic acid of giving birth to is less, and the painted effect that prevents that free carbonic acid produced is also less, at this moment, adds free carbonic acid in the time of can be with carbonate.The add-on of free carbonic acid comprises the secondary free carbonic acid of giving birth to, and is that 0.1-50wtppm is preferably 1-30wtppm to crystalline adduct.When in the presence of carbonate crystalline adduct being done heating and dissolve, it dissolves temperature is 115-180 ℃, is preferably 120-150 ℃, and dissolving pressure is 1-5atm, is preferably 0.1-1.9atm.The air conditions that dissolves, the alap air conditions of oxygen concentration preferably, usually, oxygen concentration is below the 0.005vol%, to be preferably in below the 0.001vol%.In addition in the present invention, in order to make the crystalline adduct dissolving at short notice, just should use and resemble the above-mentioned refining phenol, almost non-staining hot phenol dilutes dissolving to this crystalline adduct, also can adopt such method, that is: make it to be dissolved in the liquid that dissolving of crystalline adduct finished.

In the present invention, be that the heating melt to the crystalline adduct of having added aliphatic carbonate carries out evaporation process, the evaporation process of this occasion is the condition of 130-200 ℃ of decompression.Comparatively ideal evaporation process is that the temperature of melt integral body is in below 185 ℃, and makes at least a portion of melt accept heating under the temperature more than 160 ℃.If the temperature of evaporation process is too low, so when strongly-acid material and aliphatic carbonic acid reactant salt the coloring effect of secondary aliphatic carbonic acid of giving birth to just can not give full play to, on the other hand,, will cause the painted decomposition of aliphatic carbonic acid so if this temperature is too high.This evaporation process is under reduced pressure carried out, and this pressure is 100 holders, is preferably the 5-40 holder.In addition, the air conditions of evaporation process is the alap situation of oxygen concentration, and usually, oxygen concentration is below the 0.005vol%, but is preferably below 0.001%.

According to the present invention, can obtain purity height, form and aspect good and when dissolving, can prevent painted finished product dihydroxyphenyl propane.In addition, this material has storage stability preferably.

(the 4th process)

Below will illustrate for obtaining the 4th process of dihydroxyphenyl propane of the present invention.

Employed crystalline adduct among the present invention, it dissolves look APHA below 15, is preferably in below 10, and such crystalline adduct can obtain by following way:

The phenol solution that contains dihydroxyphenyl propane is made the multistage partial crystallization to be handled.Also can obtain by such method: the phenol solution that contains dihydroxyphenyl propane is done the crystalline adduct that obtains after partial crystallization is handled with above-mentioned coloration reason the refining phenol that has been removed of material clean.Being applicable to crystalline adduct of the present invention, is to be the material shown in the 1st, the 2nd and the 3rd process aforementioned of the present invention that obtains dihydroxyphenyl propane.

The crystalline adduct that obtains as stated above, with having comprised that dissolving device series device and evaporation unit, that remove phenol from crystalline adduct handles, in the present invention, then before this is handled, should remove the oxygen that is attached to material (this material constituted phenol remove included in the device be to dissolve wall within device and the evaporation unit at least) surface in advance.

The above-mentioned inner-wall surface that dissolves device and evaporation unit is a metal material, is generally stainless steel, and for example SUS304, SUS316,316L etc. on its surface, adhere to usually in conjunction with 1m ²In the oxygen of 30～60 mmoles is arranged.The amount of this oxygen can be measured by various methodologies.For example can adopt test film and according to cleaning condition and surface (by its degree of depth of surface erosion determined) relation of adhering between the conjugate oxygen amount infers.Also can and clean with the relation between phenol painted and measure from the conjugate oxygen amount of surface attachment.In addition, under other the occasion of scavenging solution, also can be according to it relation between the painted and surface attachment bonded oxygen amount measure.For example, the painted situation of phenol is: for the oxygen of millionth weight, can form 6APHA, therefore such mensuration relation just can be used.Research according to the present inventor, these dissolve device and evaporation unit, when after removing the oxygen that its inner wall surface adheres in advance, using, because of crystalline adduct dissolve with the dissolution liquid evaporation process time heating material that produce, that constitute coloration reason just obtained significant inhibition, so just can obtain the good finished product bis-phenol of form and aspect.

From dissolving within device and the evaporation unit wall when removing deoxidation, can realize as clean inner-wall surface through organic solvent.As organic solvent, can use the mixture of phenol or dihydroxyphenyl propane, phenol and dihydroxyphenyl propane.The clean temperature is 100～200 ℃, be preferably 120～185 ℃, surrounding gas condition during cleaning is non-oxidizing gas concrete conditions in the establishment of a specific crime such as nitrogen and argon gas, Guang gas, steam, can use decompression, the concentration of the oxygen in this gas is below the 0.01vol%, being preferably below the 0.005vol%, is below the 0.001vol% better.Cleaning with organic solvent is done inner-wall surface can realize by internal wall jet organic solvent by nozzle.After cleaning with organic solvent, just discharge, in case of necessity, also can carry out drying inside being trapped in the organic solvent that dissolves device and evaporation unit bottom.Yet the mensuration of oxygen concentration of gas phase is normally utilized the analysis meter by the micro amount of oxygen of gas chromatography or electrochemical process.

When removing the processing of deoxidation, attached to the oxygen level of this inner-wall surface be: inner-wall surface 1m from above-mentioned inner-wall surface ²Be below 10 mmoles, be preferably below 5 mmoles.

As the molten device that dissolves, can use the hermetic type container of the indirect heating formula that heating jacket has been installed on its outside wall surface and within it portion the inside heating-type hermetic type container of heating tube has been installed.As evaporation unit, can use distillation tower, desorption apparatus, centrifugal-film evaporator etc.

Be provided with pipe arrangement dissolving between device and the evaporation unit, in evaporation unit, be provided with the vent pipe of dihydroxyphenyl propane.In the present invention, even at the inner-wall surface of these pipe arrangements, also can similarly implement deoxygenation and handle with above-mentioned.

In the present invention, foregoing, be to dissolve device and evaporation unit at least to installing included in the series, can implement deoxygenation to the oxygen that adheres in the inner wall surface thereof and handle.Then, this device series is sent into crystalline adduct, in dissolving device, dissolve this crystalline adduct, in evaporation unit, the dissolution liquid that is obtained is made evaporation process again, thereby remove phenol through evaporation.

As the operational condition that dissolves device, temperature is 115～180 ℃, is preferably 120～150 ℃, and pressure is normal pressure, and the concentration of oxygen is below the 0.01vol%, be preferably below the 0.005vol%, and be below the 0.001vol% better.Evaporation unit can adopt one or more snippets, this evaporation unit of 1 section under the situation of 1 section of use, and the operational condition of the evaporation unit of this terminal section under the multistage situation about using is 180～200 ℃, preferably 170～185 ℃, pressure is 1～100 holder, preferably 5～40 holders, the oxygen concn in the gas phase is below the 0.005vol%, to be preferably below the 0.001vol%.

According to the present invention, can suppress the generation of the coloring material that causes because of heating (to dissolving and heating during to the evaporation process of this dissolution liquid of crystalline adduct) significantly, thereby can obtain the high dihydroxyphenyl propane of the good purity of form and aspect.

(the 5th process)

Below, will illustrate for obtaining the 5th process of dihydroxyphenyl propane of the present invention.

Employed in the present invention crystalline adduct can be used the various crystalline adduct shown in the invention described above the 4th process (for obtaining shown in the dihydroxyphenyl propane).

Be used as the crystalline adduct of raw material among the present invention, after dissolving, be introduced into the evaporation process that is constituted by evaporator tower (its inside is provided with the parts that evaporation surface is improved at least) here, remove phenol through evaporation with the phenol of paying or being accompanied by.In the present invention, before can beginning in the running of evaporator tower, remove oxygen in advance attached to relevant parts (making the inner-wall surface of evaporator tower and the parts that evaporation surface improves) surface.

The parts that the inwall of evaporator tower and evaporation surface are improved have the metallic surface that for example constitutes filler and canopy section, are generally stainless steel, formed surfaces such as SUS304, SUS316, SUS316L for example, and on this surface, 1m normally ²In adhere to the oxygen that combines 30～60 mmoles.Research according to the present inventor, remove attached to the oxygen of these metallic surfaces in advance and when using evaporator tower, just can suppress the coloring material that the heating because of the evaporation process of crystalline adduct generates significantly, so just can obtain the product dihydroxyphenyl propane that the good and form and aspect of form and aspect have been suppressed through the variation of time.

From the inner-wall surface of evaporator tower and can improve the operation that deoxidation is removed on the surface (for example filling surface) of evaporation surface, can be with organic solvent by its surface be realized as clean.As having of organic solvent: phenol and or the mixture of dihydroxyphenyl propane, phenol and dihydroxyphenyl propane.The temperature of clean is 100～200 ℃, is preferably 120～185 ℃.Surrounding gas during cleaning is reactive gas not, for example nitrogen, argon gas or degassing steam, and the concentration of oxygen is below the 0.1vol%, to be preferably below the 0.05vol% in the surrounding gas.

The cleaning of carrying out to the inner-wall surface of evaporator tower and for the parts surface that evaporation surface is improved with organic solvent, can be by realizing at its jet surface organic solvent (being undertaken) by nozzle, in addition, also can realize by circulation organic solvent in evaporator tower.

In the said in the above deoxygenation treating processes, at the inwall of evaporator tower and be the oxygen of the surface attachment that makes the parts that water surface of evaporation improves, at the 1m of its surface-area ²In be below 10 mmoles, be preferably below 5 mmoles.

In the present invention, above-mentioned deoxygenation handle applicable at evaporator tower inner-wall surface and for making the surface of the parts that evaporation surface improves, in addition, the surface of also applicable other metal that is contacted at crystalline adduct dissolution liquid or dihydroxyphenyl propane, for example applicable for make the inner-wall surface that dissolves device that crystalline adduct dissolves and dissolve device and evaporator tower between the inner-wall surface of pipe arrangement, moreover applicable to be arranged in the evaporator tower, dihydroxyphenyl propane draws the inner-wall surface of pipe arrangement.

In the present invention, crystalline adduct is heated to dissolve to become and then is supplied to evaporator tower after the dissolution liquid, removes phenol through evaporation here.

The device that dissolves as crystalline adduct has the outside wall surface indirect heating formula hermetic type container of heating jacket is housed, and the inside heating-type hermetic type container that heating coil is housed in inside is also arranged.

Operational condition when dissolving crystalline adduct generally is that temperature is 115～180 ℃, is preferably 120～150 ℃, and pressure is 1.0～5.0atm (absolute pressure), is preferably 1.0～1.9atm (absolute pressure).In addition, crystalline adduct is when dissolving, and concentration of oxygen is below the 0.005vol%, preferably to be maintained at below the 0.001vol in the surrounding gas.In addition, in the present invention, in order to dissolve this crystalline adduct at short notice, will with as above-mentioned refining phenol, almost non-staining hot phenol dilutes and dissolves, also can make it to be dissolved in the liquid that dissolving of crystalline adduct be through with.

As evaporator tower, inner wall surface thereof is metal material, especially stainless steel at least, formed inner barrel such as SUS304, SUS316, SUS316L for example, and be provided with parts that evaporation surface is improved in this inside.This evaporator tower can be provided with heater means in its bottom.As the parts that evaporation surface is improved, can use filler and the frame section and the firm wall of known technology, these things can also can make up separately and use.At this moment, the shape material of filler, frame section, firm wall by metallic substance, for example can be made of the stainless steel of SUS304, SUS316, SUS316L etc.In addition, as filler Raschig ring, Pall ring, plate body, porous plate etc. are arranged, the dish of frame section is the device that is provided with downtake for bubble bell, porous template, this dish.

Evaporator tower is at least one, preferably by making up more than 2.This evaporator tower can be the evaporator tower (steam desorb evaporator tower) that adopts steam.The ideal evaporation process of the dissolution liquid of crystalline adduct of the present invention is the common evaporator tower that does not use steam and use the use that combines of the steam desorption tower of steam.

Below, will illustrate and adopt evaporating (the 2nd evaporator tower by the 1st evaporator tower that does not use steam and use steam is constituted) to come the crystalline adduct dissolution liquid is done the method for evaporation process.

In this evaporation process method, the dissolution liquid that dissolves device from crystalline adduct is introduced the 1st evaporator tower, under the situation that does not have steam, make evaporation process here, thereby remove a part of phenol in this solution with the condition of decompression.Come Separation and Recovery to contain the steam of phenol from the cat head of the 1st evaporator tower, then the separated dissolution liquid of having removed of Separation and Recovery part phenol again from its bottom.Bottoms from the 1st evaporator tower is introduced into the 2nd evaporator tower, here in the existence of steam down and carry out evaporation process under reduced pressure, phenol remaining in the dissolution liquid is removed through evaporation again.From the 2nd evaporator tower, can discharge the vapour mixture that contains phenol, steam and a small amount of dihydroxyphenyl propane as its overhead materials, as its bottoms, separablely reclaim out highly purified dihydroxyphenyl propane.

Do not use the operational condition of the 1st evaporator tower of steam to be, temperature is 125～200 ℃, is preferably 130～185 ℃, and pressure is below 100 holders, is preferably 5～40 holders.The concentration of the oxygen in the steam gas in the evaporator tower is below the 0.005vol%, preferably to be maintained at below the 0.001vol%.In the 1st evaporator tower, 95～99.8 weight % of the phenol that exists in the crystalline adduct solution, preferably 98～99.7 weight % are removed through evaporation.

Operational condition as the 2nd evaporator tower that uses steam is that temperature is 130～200 ℃, be preferably 160～185 ℃, pressure is below 100 holders, is preferably 5～40 holders, the feed rate of the steam during dihydroxyphenyl propane dissolution liquid 1Kg is 0.02～0.2kg, is preferably 0.04～0.1kg.The concentration of oxygen is below the 0.005vol%, preferably to be maintained at below the 0.001vol% in the interior steam gas phase of evaporator tower.In the 2nd evaporator tower, the whole in fact amount that derives from the phenol in the crystalline adduct dissolution liquid of the 1st evaporator tower is evaporated removes, as bottoms, can obtain the phenol containing ratio below 200wtppm, be preferably the following dihydroxyphenyl propane of 50wtppm.

The mixing steam of steam and a small amount of dihydroxyphenyl propane be can obtain containing from the 2nd evaporator tower that uses steam, but can from this mixing steam, Separation and Recovery phenol and dihydroxyphenyl propane be gone out.Come Separation and Recovery phenol and dihydroxyphenyl propane from this mixing steam, can implement with existing known method.But preferably use in the present invention, the condensation method of the desorption gas that is constituted by the 2nd refrigerating work procedure described later.

According to the present invention, be under the condition of decompression and use the big evaporator tower of evaporation surface to come the dissolution liquid of crystalline adduct is carried out evaporation process, so just improved the efficient of evaporation process.And under this occasion, should use in advance from its surface (wall and the inner parts that are provided with within it) as evaporator tower have made the device that deoxygenation is handled, so just can reduce the growing amount of the coloring material that causes because of the evaporation of dissolution liquid heating significantly, so the bisphenol A with high purity that the form and aspect that just can obtain form and aspect excellence and dissolution liquid have significantly been reduced through the variation of time.

(the 6th process)

Below will illustrate for obtaining the 6th process of dihydroxyphenyl propane of the present invention.

Employed crystalline adduct is to be related various crystalline adduct in the 4th process that obtains the invention described above that dihydroxyphenyl propane shows among the present invention.

Below, by reference Fig. 6 the 6th process of the present invention is described.

In Fig. 6,1,2 and 3 expression thin-film evaporators.This vaporizer is the structure that the film of perisporium formation within it makes it to evaporate by indirect heating.

Can use its inside to be provided be rotated in this centrifugal-film evaporator that its internal perisporium face form liquid film of the rotation wing in the present invention by this rotation wing.

In addition, in Fig. 6,4 for being attached to the external heater on each thin-film evaporator.This well heater normally its internal circulation the chuck of heating medium.

In the present invention, the crystalline adduct of using as raw material is dissolved by heating or by the refining diluted dissolving of phenol, it is a kind of phenol solution that contains dihydroxyphenyl propane.Be applicable to that phenol solution of the present invention is, have APHA and be form and aspect below 15, bisphenol A concentration at 50～80 weight %, be preferably in the material of 60～70 weight %.

This raw material phenol solution is introduced into the 1st thin-film evaporator (hereinafter to be referred as vaporizer) from pipeline 10, phenol solution as liquid film when the vaporizer internal perisporium flows down, be heated by external heater 4, so the steam that contains phenol and dihydroxyphenyl propane is discharged from by pipeline 11.By this steam is carried out condensation with regard to recyclable phenol and dihydroxyphenyl propane.

The temperature of the phenol solution by pipeline 10 is preferably 120～150 ℃, and the temperature of the 1st vaporizer 1 is 160～185 ℃, is preferably 165～175 ℃, and its pressure is 15～60 holders, is preferably 15～30 holders.

In the 1st vaporizer,, be introduced into the 2nd vaporizer 2 again by being drawn through pipeline 12 to make the raffinate (dihydroxyphenyl propane) that evaporation process obtains as the phenol solution of raw material.The temperature of the evaporation raffinate of the phenol solution by pipeline 12 is preferably 170～185 ℃.In addition, the phenol concentration that constitutes in the dihydroxyphenyl propane of this raffinate is 1～5 weight %.

In the 2nd vaporizer 2, dihydroxyphenyl propane contacts do convection current with the steam, the desorption gas (being made of phenol and dihydroxyphenyl propane) that draw from the 3rd vaporizer, is heated by external heater 4, is discharged from by pipeline 13 so contain the desorption gas of phenol, dihydroxyphenyl propane and steam.

Temperature in the 2nd vaporizer 2 is preferably 170～185 ℃, and pressure is below 15 holders, is generally below 10～15 holders.

The evaporation raffinate that obtains in the 2nd vaporizer 2 has been introduced into the 3rd vaporizer by pipeline 14, and the temperature of this raffinate is preferably 170～185 ℃, and the concentration of phenol is 0.05～0.10 weight % in the dihydroxyphenyl propane of formation raffinate, is preferably 0.05-0.07 weight %

In the 3rd vaporizer 3, contact do convection current with 15 steam that are introduced into by the road from the dihydroxyphenyl propane of the 2nd vaporizer 2, be heated by external heater 4, and this desorption gas drawn by pipeline 17, then, this desorption gas smokes gas and is directed to the 2nd vaporizer 2 as separating.Temperature in the 3rd vaporizer is 170～185 ℃, and pressure is below 15 holders, is generally 10～15 holders.The steam that is introduced into the 3rd vaporizer 3 from pipeline 15 is for by the road 14 and be introduced into for the dihydroxyphenyl propane of the 3rd vaporizer 3, is by weight more than 3 weight %, is preferably 4～6 weight %.Desorption gas by pipeline 17 consist of phenol: 0.8～1.2 weight % is preferably below the 1 weight % dihydroxyphenyl propane: 5～7 weight %, all the other are steam.

The highly purified dihydroxyphenyl propane that is obtained in the 3rd vaporizer 3 is drawn by pipeline 16.This dihydroxyphenyl propane, the containing ratio of phenol are 0.005 weight %, and form and aspect APHA is high-grade material below 20.

From the 2nd vaporizer 2 by the road 13 derivative desorption gas accept condensation process, so, contained phenol and the separated recovery of dihydroxyphenyl propane in this gas.This desorption gas can carry out condensation process with existing known method, especially preferably uses the condensing method (being made of 2 stage refrigerating work procedures described later) of desorption gas.

In the present invention, at first be to adopt the 1st thin-film evaporator that the phenol solution that contains dihydroxyphenyl propane (derived from dihydroxyphenyl propane, phenol crystal adduct) is carried out evaporation process, so can obtain the dihydroxyphenyl propane that the phenol containing ratio is 1～5 weight %.In the present invention, owing to make the temperature of the 1st thin-film evaporator remain on 160～185 ℃, make pressure remain on 15～60 holders, therefore, even produced the cooling that the rapid evaporation because of phenol causes, also can not separate out dihydroxyphenyl propane, so just can successfully implement this evaporation process.

In addition, in the present invention, for the dihydroxyphenyl propane that obtains with aforesaid method, removing for wherein contained phenol is done evaporation, then is to adopt thin-film evaporator to carry out desorb to handle.Under occasion of the present invention, phenol amount in this dihydroxyphenyl propane is 1～5 weight %, and 2 thin-film evaporators are being contacted using, so can make the temperature of this vaporizer remain on 170～180 ℃, and remain under the following high vacuum of 15 holders, thereby remove phenol in this dihydroxyphenyl propane, so can obtain that form and aspect are good, the bisphenol A with high purity of the containing ratio of phenol below 0.005 weight % through evaporation.

In order to obtain the dihydroxyphenyl propane of form and aspect excellence, the temperature in the time of should making evaporation process (evaporation process that the phenol solution that contains as the dihydroxyphenyl propane of raw material is carried out) remains on below 185 ℃, thereby suppresses the generation of coloring impurities such as different allyl phenol.In occasion of the present invention, can remain on the temperature of this evaporation process below 185 ℃, through evaporation phenol is removed fully, so resulting dihydroxyphenyl propane is that form and aspect APHA is at the high purity substance below 20.

Moreover, in the present invention, be as stripping steam, so can obtain the such advantage of phenolysis suction effect raising of the 2nd thin-film evaporator the desorption gas that is constituted by steam (containing the phenol and the dihydroxyphenyl propane that are generated in the 3rd thin-film evaporator) at the 2nd thin-film evaporator.

According to evaporation process of the present invention, the available on the whole extremely short residence time (being generally 60～180 seconds) operates, and therefore, its efficient is very high.Especially under occasion of the present invention, preferably the 1st thin-film evaporator, the 2nd thin-film evaporator and the combination in order of the 3rd thin-film evaporator, make it to flow to the below by the fluidic run by gravity from the top, then can prevent the generation of block effectively, and can shorten the residence time of liquid in device is serial.

(the 7th process)

Below, illustrate for obtaining the 7th process of dihydroxyphenyl propane of the present invention.

In the present invention, as the having of crystalline compounds, related in the 1st process of the invention described above (dihydroxyphenyl propane illustrates in order to obtain), in fact be in neutrallty condition, dissolve look at the material that is preferably in below the 15APHA below the 10APHA.

In the present invention, adopt thin-film evaporator, substantially under the condition of anaerobic and decompression, to contain dihydroxyphenyl propane (from be in fact neutrallty condition, dissolve form the crystalline adduct of look below 15APHA) solution evaporate, thereby remove wherein phenol.At this moment, so-called oxygen free condition in fact is meant that the concentration of removing gas oxygen in the device series of phenol for evaporation is 0.005volppm.Be in the condition of anaerobic in fact in the device series in order to make, can be in device series to nitrogen and argon gas etc. not reactive gas make purifying, better is the decompression operation that can carry out device repeatedly, reactive gas is not made purification process in the device under reduced pressure.

According to the present invention, from the solution that contains dihydroxyphenyl propane (from specific crystalline adduct, forming), remove phenol through evaporation, can add the painted agent that prevents in case of necessity.This is painted to prevent that agent may be added directly in the crystalline adduct, and at this moment painted prevents that agent can be added the crystalline adduct that is mixed to random order, promptly pulverulence, dissolve in state, slip state or the solution state.

Be applicable to the painted aliphatic carbonic acid that is that prevents agent of the present invention.This aliphatic carbonic acid demonstrates such effect: make the dihydroxyphenyl propane of the state of dissolving and atmosphere make Long contact time, so the variable color of the dihydroxyphenyl propane can prevent to remain on high temperature the time.

As aliphatic carbonic acid, so long as can demonstrate the painted effect that prevents, then not being subjected to the restriction of its kind to dihydroxyphenyl propane, can use to be the known material of people.As this class material, can list: formic acid, oxalic acid, citric acid, tartrate, glycol acid, lactic acid, oxysuccinic acid, glycerol acid etc.These materials can produce when the temperature more than 160 ℃ in reaction and decompose or the appearance opposite sexization, but have shown then that for dihydroxyphenyl propane excellent painted preventing acts on.The addition of aliphatic carbonic acid is 1～100 ppm by weight to crystalline adduct, is preferably 5～50 ppm by weight.

By the adding of aliphatic carbonic acid, can prevent product dihydroxyphenyl propane painted, good thermal stability in the time of can obtaining to dissolve.

Can be according to implementing with the same mode of the invention described above the 6th process (adopting device shown in Figure 6).

(the 8th process)

Below illustrate for obtaining the 8th process of dihydroxyphenyl propane of the present invention.

The parsing gas that is used as the raw material use in the present invention is the gas that is obtained when with steam the mixture of phenol and dihydroxyphenyl propane being done desorb, and it is made of phenol, dihydroxyphenyl propane and steam.As having of this parsing gas, row is from the desorption gas of pipeline shown in Figure 6 13.

In the present invention, desorption gas is supplied to first refrigerating work procedure under decompression state, here makes it to contact and realize cooling with the 1st heat-eliminating medium (being made of phenol or the phenol that contains dihydroxyphenyl propane) do convection current.The 1st refrigerating work procedure should make the dihydroxyphenyl propane in the desorption gas in fact all be dissolved in the heat-eliminating medium.Steam in the stripping gas is condensed in the 1st refrigerating work procedure hardly, but is sent to the 2nd refrigerating work procedure.Phenol in the stripping gas, its part is condensed in the 1st refrigerating work procedure, and remaining uncooled part is sent to the 2nd refrigerating work procedure with steam.The phenol that comes out from the stripping gas Separation and Recovery in the 1st refrigerating work procedure and the mixed solution of dihydroxyphenyl propane, its part can be used as heat-eliminating medium.The temperature of the 1st heat-eliminating medium exceeds 1-50 ℃ than the zero pour of phenol.The rate of recovery of the phenol in the 1st refrigerating work procedure accounts for more than the 70 weight % of the whole phenol that are supplied to the 1st refrigerating work procedure, is preferably in more than the 85 weight %.

The consumption of employed heat-eliminating medium in the 1st refrigerating work procedure, as long as can be cooled to stripping gas temperature requiredly, usually the weight ratio for stripping gas is 5-10, is preferably 5-6.In addition, contained dihydroxyphenyl propane is 0.05-0.20 to the weight ratio of phenol in the bis-phenol in having dissolved stripping gas (being obtained in the 1st refrigerating work procedure) and the heat-eliminating medium of phenol, is preferably 0.08-0.14.In the 1st refrigerating work procedure,,, also can not cause the crystalline adduct partial crystallization of dihydroxyphenyl propane and phenol to come out even cooling temperature is below the zero pour of dihydroxyphenyl propane so owing to exist excessive phenol in the dihydroxyphenyl propane.

The pressure of the 1st refrigerating work procedure is preferably the 5-20 holder below 30 holders, it should be corresponding with the pressure in the 2nd thin-film evaporator 2.In addition, the temperature in the 1st refrigerating work procedure should be able to make steam remain gas under above-mentioned pressure condition and make the part of phenol remain the temperature of liquid.Comparatively ideal temperature (can make the temperature of dihydroxyphenyl propane condensation) should exceed 1～50 ℃ than the zero pour of phenol, and its cooling temperature is 42～90 ℃, is preferably 45～55 ℃.

Thereby the mixed gas of the steam that is sent to the 2nd refrigerating work procedure and phenol here contacts do convection current with the 2nd heat-eliminating medium that the aqueous solution by phenol constitutes and realizes cooling.The 2nd refrigerating work procedure should be that the steam that is sent to this operation and whole in fact amount of phenol are changed by condensing (condensation), thereby, from this operation, reclaim the aqueous solution of phenol.The aqueous solution of the phenol that is obtained in the 2nd refrigerating work procedure, its part can be used as the 2nd heat-eliminating medium and use.In the aqueous solution concentration of phenol by stripping gas form and the condition of the 1st refrigerating work procedure is determined, be generally 55～75 weight %.In addition, the temperature of the 2nd heat-eliminating medium is to hang down 1～10 ℃ than the condensing temperature of steam.

The amount of employed the 2nd heat-eliminating medium in the 2nd refrigerating work procedure is as long as can make the abundant amount of whole amount condensations of mixed gas.Usually, with weight ratio from the mixture of the steam of the 1st refrigerating work procedure and phenol be 100～300, be preferably 190～250 ℃.Pressure in the 2nd refrigerating work procedure is below 30 holders, is preferably 5～20 holders, should be corresponding with the pressure of the 1st refrigerating work procedure.Cooling temperature in the 2nd refrigerating work procedure (vapor condensation temperature) is as long as can make steam under the above-mentioned pressure condition and the whole condensation liquefactions of mixed gas of phenol.

Used water cooler in the 1st and the 2nd refrigerating work procedure, so long as gas-to-liquid contact type device gets final product, its kind is unrestricted.As for example having of this class water cooler, packing tower, spray column etc.Using under the occasion of packing tower, as its filler, should be able to accomplish to suppress the pressure-losses, can use Raschig ring, Pall ring, encircle metal sheet etc. more.In addition, as employed water cooler in the 1st and the 2nd refrigerating work procedure, can be provided with respectively, also can be a tower device that contains 2 water coolers.

Hereinafter with reference to drawing, the enforcement state of one of condensation processing method of above-mentioned stripping vapor is described.

In Fig. 7,21 is the 1st water cooler, and 22 is the 2nd water cooler.Pipeline 3 is the stripping gas pipelines that are connected in the above-mentioned pipeline 13 shown in Figure 6.Pipeline 24 is for being connected the vacuum-lines on off-gas pump (not shown) and the water cooler, and the full device series that contains water cooler is maintained under the reduced pressure.

Desorption gas is supplied to the bottom of the 1st water cooler 21 by pipeline 23, here; Contact do convection current with the 1st heat-eliminating medium that has been introduced into from the 1st water cooler top by pipeline 25 (phenol or contain the phenol of dihydroxyphenyl propane).The heat-eliminating medium that is dissolved with the dihydroxyphenyl propane that has been condensed in the 1st water cooler and phenol is by comprising that the pipeline 26 of drawing pump (discharging pump) 27 is drawn from the bottom of the 1st water cooler.By these pipeline 26 derivative heat-eliminating mediums, in case of necessity, to its part be cooled to temperature required after, be re-used as heat-eliminating medium and be recirculated to pipeline 25.

Be fed to the bottom of the 2nd water cooler 22 by the mixed gas of pipeline 28 derivative steam and phenol from the top of the 1st water cooler 21, here, contact do convection current with the 2nd heat-eliminating medium (aqueous solution of phenol) that is introduced into from the top of the 2nd water cooler by pipeline 29.In the 2nd water cooler, the liquefaction that is condensed of the mixed gas of steam and phenol, then, this phlegma is drawn by the pipeline 31 that contains pump 31 from the bottom of the 2nd water cooler 22 with heat-eliminating medium, this part is by pipeline 33, after the water cooler of using by heat-eliminating medium 34 is cooled, be recirculated to the 2nd water cooler by pipeline 29 again.Containing by the road, the nubbin of the heat-eliminating medium of 30 derivative condensed steams and phenol is led to outside the system by pipeline 32.

Below, according to the condensation process method of above-mentioned desorption gas, the flow process when using a tower refrigerating unit (including the 1st water cooler and the 2nd water cooler) is made an explanation at Fig. 8.

In Fig. 8,50 are provided with a tower cooler device of the 1st water cooler 21 and the 2nd water cooler 22 for its inside.This refrigerating unit, having set its middle body between the 1st water cooler 21 and the 2nd water cooler 22 has the dividing plate of opening, so just formed in the upright structure of having established cylindrical shell 43 of its peristome.In this device, formed the ring-type hollow chamber between the inner-wall surface of the peripheral surface of cylindrical shell 43 and refrigerating unit 50, it is used to store liquid.The 42nd, make the liquid that flows down the 2nd water cooler 22 be directed into the guide plate of aforementioned ring-type hollow chamber.Tubular space 44 is the gas passage.

Yet the symbol among Fig. 8 is identical with the symbolic significance shown in Fig. 7.In addition, in Fig. 8, flow control shown in Figure 7 does not obtain expression.

According to the condensation processing method of above-mentioned desorption gas, be not desorption gas to be carried out boost, but it is condensing to carry out cooling under the decompression state below 30 holders.And, although at this moment be to use the following low pressure of 30 holders and be corresponding with it low vapor condensation temperature, also can not separate out the crystallisate of any dihydroxyphenyl propane and phenol.Therefore, in the condensing facture of this desorption gas, can not occur that the chiller efficiency that causes reduces and the trouble of water cooler obturation because of solid is separated out.

In addition, according to the condensation process method of above-mentioned desorption gas, the steam, phenol and the dihydroxyphenyl propane that constitute desorption gas all are condensed, and these gases do not flow into vacuum evacuating system in fact.So the vacuum exhaust pump only is that the handle assembly system remains under the required reduced pressure, only needs the little pump of swept volume to get final product, therefore, to the reduction of equipment cost and energy-conservation be very favorable.

[embodiment]

Below, will come the present invention is described in detail according to embodiment.

A: the process for purification of crystalline adduct,

Embodiment 1

To commercially available industrial phenol (moisture concentration 0.1wt%, impurity concentration 0.05wt%), under 8 ℃ temperature, the Combe, George Alexander made from ロ-system ア Application De Ha-ス company draws special ion exchange resin IR-118H ⁺Resin, with contacting processing 50 minutes duration of contact, the temperature of base product is 175 ℃, tower top pressure is 560 holders, has just obtained to dissolve the refining phenol that look is 6APHA after distilling.

On the other hand, the mixture that obtains after making phenol and acetone contacts in the presence of acid catalyst, dissolve dihydroxyphenyl propane, phenol and impurity that look is 50APHA is also by partial crystallization, thereby separates out crystalline adduct.

Then, make filtration under diminished pressure, thereby just obtain solid shape crystalline adduct by slip to this crystalline adduct.Then, with the refining phenol of above-mentioned acquisition,, clean with the ratio of 2.5 weight unit to this crystalline adduct of 1 weight unit.To the crystalline adduct of acquisition like this pressure in 175 ℃ and 25 holders, carry out the steam parsing with 30 minutes times, after substantially being removed fully, phenol just obtained dihydroxyphenyl propane.This dihydroxyphenyl propane to dissolve look (APHA) be 15, be the fabulous materials of form and aspect.Dissolving look (APHA) number measures according to ASTMD1686 Standard Test Method for Color of Solid AromaticHydrocarbons and Related Materials in the Molten State.

Comparative examples A-1

The mixture of the dihydroxyphenyl propane, phenol and the impurity that dissolve look 50APHA is made partial crystallization handle, thereby separate out crystalline compounds.Then, the slip of this crystalline adduct is made filtration under diminished pressure, thereby obtain solid shape crystalline adduct, again a part is wherein decomposed under 190 ℃ temperature, thereby reclaim phenol.With this phenol remaining crystalline adduct 1 weight unit is cleaned with the ratio of 2.5 weight.To cleaning of acquisition like this crystalline adduct, under the conditions of 175 ℃ and 25 holders, carry out water vapor desorption with 30 minutes times, thereby substantially whole amounts of phenol removed, obtain dihydroxyphenyl propane at last.The look that dissolves of this material is 20APHA.In addition, to this dihydroxyphenyl propane, be 80APHA dissolving back maintenance form and aspect in the time of 5 hours under atmosphere.

Comparative examples A-2

Except when refining phenol is done distillation, the base product temperature is beyond 200 ℃, and other is all identical with embodiment A-1, thereby has obtained phenol.The scavenging solution of this phenol as crystalline adduct used, according to the method identical with embodiment A-1, thereby obtain dihydroxyphenyl propane, the look that dissolves of this material is 30APHA.

Dissolve look during 175 ℃ of the dihydroxyphenyl propane that in aforementioned enforcement A-1 and Comparative examples A-1～A-2, obtains, be indicated in the following table

[Table A-1]

Numbering	Dihydroxyphenyl propane dissolve look (APHA)
		Embodiment A-1	15
Comparative examples A-1	20
		Comparative examples A-2	30

Embodiment A-2

Is the industrial phenol of 430wtppm to moisture concentration for the 0.07wt% impurity concentration, and under the duration of contact of 80 ℃ temperature and 20 minutes, the Combe, George Alexander made from ロ-system ア Application De Ha-ス company draws special IR-118+ resin to distill, thereby obtains refining phenol.

Comparative example 3

Except using moisture concentration as 0.73wt%, the industrial phenol of impurity concentration as 430wtppm, other all according to embodiment 2 the same experiments.

Like this proterties of the refining phenol that obtains, the proterties with as the industrial phenol and the phenol after the ion exchange resin treatment of raw material is indicated on Table A-2.

[Table A-2]

Numbering	Project	Primary industry phenol	Phenol behind the ion exchange resin	The phenol after the processing is stayed in steaming
					Embodiment A-2	Impurity benzofurane form and aspect	43wtppm (310wtppm) 20APHA	1205wtppm (not measuring) 30APHA	5wtppm (not measuring) 5APHA
Comparative examples A-3	Impurity benzofurane form and aspect	430wtppm (310wtppm) 20APHA	796wtppm (42wtppm) 30APHA	115wtppm (25wtppm) 10APHA

Embodiment A-3

TREATMENT OF ION EXCHANGE RESINS shown in the embodiment A-2 was carried out 1000 hours continuously, at this moment just can measure the benzofurane class of having represented the compound of impurity in the phenol after the processing.

Embodiment A-4

Phenol and acetone are reacted, from the resultant of reaction that is obtained, evaporate nearly all generation water and a part of phenol then, so obtain to dissolve the dihydroxyphenyl propane that look is 50APHA and the mixture of phenol and impurity, this mixture done just to have separated out crystalline adduct after partial crystallization is handled.The slip of this crystalline adduct is made filtration under diminished pressure with the refining phenol that the aftermentioned method obtains, use the ratio of 2.5 weight unit with the adducts of 1 weight unit and clean.The crystalline adduct of acquisition like this under the condition of the pressure of 175 ℃ temperature and 25 holders and 30 minutes, is carried out water vapor desorption, thereby removed phenol in fact fully, obtain dihydroxyphenyl propane at last.This dihydroxyphenyl propane has shown the look that dissolves of 10～15APHA, and is the fabulous materials of form and aspect.In addition, maintenance is in the time of 5 hours under atmosphere dissolving the back, and the form and aspect of this dihydroxyphenyl propane are 30APHA, can confirm that this is the low material of tint permanence.

Yet, the above-mentioned refining phenol that uses is to dissolve the material of look as 5APHA, this material is to generate like this: from resultant of reaction (reaction of above-mentioned phenol and acetone) thus be evaporated the phenol of separating and accept processed and obtain processed thing (moisture concentration is 0.1wt%), the Combe, George Alexander of producing with ロ-system ァ Application De Ha-ス company draws special IR-118H+ resin to contact processing under the duration of contact of 80 ℃ and 50 minutes then, then, in the base product temperature is 175 ℃, tower top pressure is to distill under 560 conditions of holding in the palm, thereby obtains above-mentioned substance.

B: the manufacture method of crystalline adduct

Embodiment B-1 (the 2nd process)

According to plant system drawing shown in Figure 2, from the phenol solution that contains dihydroxyphenyl propane, obtain to contain the slip of crystalline adduct, Separation and Recovery crystalline adduct from this slip.At this moment main operational condition, according to Fig. 2 in the pipeline shown in the symbol or the relation of device be expressed as followsin.

(1) one-tenth of the base feed in the pipeline 1 is grouped into

Dihydroxyphenyl propane: 22 weight %

Phenol: 74 weight %

Other: 4 weight %

(2) partial crystallization tower

(i) temperature: 54 ℃

(ii) residence time: 120 minutes

(3) be attached to micro-crystallization adducts dissolving vessel among the partial crystallization tower A

(i) temperature: 55 ℃

(ii) residence time: 6 minutes

(4) partial crystallization tower B

(i) temperature: 47 ℃

(ii) residence time: 120 minutes

(5) be attached to the dissolving vessel of the micro-crystallization adducts among the partial crystallization tower B

(i) temperature: 48 ℃

(ii) residence time: 6 minutes

In above-mentioned experiment, be 15APHA from form and aspect by isolating crystalline adduct the pipeline 35 resulting slips, the containing ratio of the micropartical composition of particle diameter below 100 μ m is 13 weight % in the crystalline adduct.

Comparative example B-1

In device shown in Figure 2, only be to use the 1st section partial crystallization tower A to make the crystalline adduct slip.At this moment, the operational condition of partial crystallization tower A is, its temperature is 47 ℃, and the temperature that is attached to the micro-crystallization adducts dissolving vessel Q among the partial crystallization tower A is 48 ℃, and other condition all situation with Embodiment B-1 is identical.

The form and aspect of resulting crystalline adduct are 30APHA in this experiment, and the ratio of the minuteness particle one-tenth branch of particle diameter below 100 μ m is 29 weight % in the crystalline adduct.

Embodiment B-2 (the 3rd process)

According to apparatus system shown in Figure 3, from the phenol solution that contains dihydroxyphenyl propane, obtain containing the slip of crystalline adduct, Separation and Recovery goes out crystalline adduct from this slip.At this moment main operational condition, according to and Fig. 3 in relation between the pipeline shown in the symbol or the device be expressed as followsin:

(1) one-tenth of the base feed in the pipeline 8 is grouped into

Dihydroxyphenyl propane: 22 weight %

Phenol: 74 weight %

Other: 4 weight %

(2) partial crystallization tower A

(i) temperature: 54 ℃

(ii) residence time: 120 minutes

(3) be attached to micro-crystallization adducts dissolving vessel 3 among the partial crystallization tower A

(i) temperature: 55 ℃

(ii) residence time: 6 minutes

According to above-mentioned experiment, in the isolating crystalline adduct, particle diameter is that the following atomic ratio of 100 μ m is 20 weight % from the slip that obtains by pipeline 20.

Embodiment B-3 (the 3rd process)

In Embodiment B-2, when making the temperature of partial crystallization tower A become 44 ℃, also the temperature head between temperature in the micro-crystallization adducts dissolving vessel 3 and the partial crystallization tower A be set at 5 ℃ moreover, the residence time of slip in jars 3 is set at 4 minutes, other all with aforementioned the same the experiment.As a result, contained in the crystalline adduct in the slip that is recovered by pipeline 20, particle diameter is that the particle component proportions below the 100 μ m is 29.5 weight %

Comparative example B-2

In Embodiment B-3, the part of the slip of drawing from the bottom of inner core 2 is not done recirculation by well heater 5 and jar 3, in addition all similarly tests with above-mentioned.Its result, contained micropartical components in proportions is 69 weight % in the crystalline adduct in the slip that is recovered by pipeline 20.

Reference example B-1 (reference example of the 5th process)

The resultant that acetone and phenol is reacted and obtain is accepted concentration, carries out partial crystallization under 50 ℃, thereby obtains the partial crystallization slip 3000g that dihydroxyphenyl propane phenol adducts is 20wt%.Under 50 ℃ the temperature this is being made filtration under diminished pressure (the mother liquor 2250g after the resulting filtration at this moment is set at A) again, resulting crystalline adduct is being made cleaning and filtering (resulting cleaning discharge opeing 580g at this moment is set at B) with refining phenol 600 grams of preparing in addition.

Crystalline adduct after cleaning is dissolved among refining phenol (APHA:5) 1310g of other preparation once more, filtration under diminished pressure under 50 ℃ temperature (the mother liquor 1430g of gained at this moment is set at C), afterwards, make 2 cleaning and filtering (clean discharge opeing to the 1st time that at this moment obtains and be set at D, be set at E) with the refining phenol 600g for preparing in addition again and clean discharge opeing to the 2nd time.

So the concentration of impurity is 100wtppm in the bis-phenol phenol crystal adduct that obtains, and dissolving look is 5APHA.

Embodiment B-4 (the 5th process)

B-1 is identical with reference example, acetone and phenol is reacted and the resultant of reaction that obtains is accepted to concentrate, and carries out partial crystallization under 50 ℃ temperature, so obtain the slurry 3000g that the dihydroxyphenyl propane phenol crystal adduct is 20wt%.Then, with the mother solution C 700g of reference example B-1, under 50 ℃, cleaning through the crystalline adduct of filtration under diminished pressure gained.The remainder 730g of the mother solution C by adding reference example B-1 with clean discharge opeing D580g the crystalline adduct after cleaning done dissolving again, under 50 ℃, carry out partial crystallization then, so obtaining the dihydroxyphenyl propane phenol crystal adduct is the slurry of 20wt%, again at 50 ℃ of following filtration under diminished pressure.Then, use the cleaning discharge opeing E580g of reference example B-1 that the crystalline adduct of gained is cleaned, do final cleaning (as final matting) with refining phenol 600g again.The concentration of impurity is identical with reference example in the crystalline adduct of the dihydroxyphenyl propane phenol that is at this moment obtained, and is 100wtppm, and to dissolve look be 5APHA.

Therefore, in the present embodiment, only be when the situation of terminal section is crucial, just use refining phenol, remaining all is to use the mother liquor that reclaims from the back segment of operation so that scavenging solution, so reduced the usage quantity of refining phenol, obtained the crystalline adduct of high-grade dihydroxyphenyl propane phenol, and then obtained high-grade dihydroxyphenyl propane.

Embodiment B-5 (the 6th process)

In the presence of an acidic catalyst,, the phenol and third bronze medal got resultant of reaction by being reacted, from this resultant, heat up in a steamer after the phenol, under 50 ℃ temperature, the concentrated solution of gained is made partial crystallization again and handle, thereby the crystalline adduct that obtains contained dihydroxyphenyl propane and phenol is the crystalline adduct slip of 20 weight %.

Then,, slurry temperature is remained under 50 ℃ the situation this is made filtration under diminished pressure, with refining phenol the crystalline adduct of gained is cleaned at last by the filter of filter cloth (eye with 106 μ m) is housed.

The following micro-crystallization adducts components in proportions of 100 μ m is 5 weight % in the crystalline adduct of this cleaning.The look that dissolves of this crystalline adduct is 10APHA, and painted impurity concentration has been significantly to reduce.In addition, the concentration of contained chroman compound (tint permanence impurity) is 100Wtppm in this crystalline adduct.

In addition, as the material that is to use various eyes of filter cloth, other are all same as described above, thus obtained particle diameter below 100 μ m, micro-crystallization adducts containing ratio has the crystalline adduct of many variations.For this crystalline adduct, measure it and dissolved the concentration of the form and aspect APHA and the chroman compound of look, its result is illustrated in B-2.

Table B-2

Experiment No	The proportion of micro-crystallization adducts composition (heavy %)	The proterties of crystalline adduct
				Form and aspect (APHA)	Chroman compound concentration (wtppm)
		1 2 3 4 5	5 10 20 35 45			10 15 20 30 40	100 110 150 230 400

From the result shown in the table B-2, can know, particle diameter becomes the crystalline adduct of ratio below 20 weight % of branch at the micro-crystallization adducts below the 100 μ m, its form and aspect excellence, and, concentration as the chroman compound of its tint permanence impurity is lower, and this is a kind of high-grade product.

C: the manufacturing of dihydroxyphenyl propane

Embodiment C-1 (the 1st process)

By in the presence of an acidic catalyst, making the reaction of phenol and acetone can obtain the mixture that constitutes by dihydroxyphenyl propane phenol and impurity, by in multistage partial crystallization operation, these mixtures being handled, just obtained dissolving look APHA and be 5, PH is 5.05 crystalline adduct.

Then, the concentration of oxygen is under the condition of 0.0010vol% in 130 ℃ temperature, the pressure of 120atm (absolute pressure) and surrounding gas, by the airtight heating container of external-heat this crystalline adduct is heated to dissolve.Then, melt to gained, be transferred to the hermetic type evaporation unit by pipe arrangement, temperature at melt is 180 ℃, the concentration of oxygen is to carry out evaporation process under the condition of 0.001vol% in the surrounding gas, and importing steam, the concentration of oxygen is to do desorb under the condition of 0.030wt% to handle in 180 ℃ and surrounding gas.

Like this dihydroxyphenyl propane that obtains, purity is more than 99.96 weight %, and the free phenol amount is 30wtppm, dissolves look APHA and be 20 form and aspect, and this is a kind of high-grade product.

Comparative example C-1

With reference to Embodiment C-1, different is: the concentration that the heating of crystalline adduct dissolves oxygen in the evaporation of operation and melt and the surrounding gas in the desorption step is 0.006vol%.Other is all identical with Embodiment C-1, thereby tests.At this moment the look APHA that dissolves that the dihydroxyphenyl propane that is obtained is showed is 65, and purity is more than the 99.96 weight %, and the free phenol amount is below the 30wtppm.

Comparative example C-2

With reference to Embodiment C-1, different is: use and syntheticly in addition to dissolve that look APHA is 20, pH is 5.05 adducts.Other is all identical with Embodiment C-1, thereby tests.The look that dissolves that the dihydroxyphenyl propane of gained is showed is 45, and purity is more than the 99.96 weight %, and the containing ratio of free phenol is below the 30wtppm.

Embodiment C-2

With reference to Embodiment C-1, different is: various variations take place in the concentration that the heating of crystalline adduct dissolves oxygen in the surrounding gas in the evaporation process of operation and melt.Other is all identical with Embodiment C-1, thereby tests.Its result is illustrated among the C-1.

Yet the BPA among the table C-1 has represented dihydroxyphenyl propane.In addition, implement N0.6 and represented comparative example.

Table C-1

Experiment No	The concentration of oxygen (vol%) in the surrounding gas			Goods BPA
							Crystalline adduct dissolves operation	Evaporization process	The steam desorption step	The form and aspect of BPA (APHA)	Free phenol among the BPA (wtlppm)	BPA purity (wt%)
	1	0.0001	With a left side	0.0002	10	＜30							＞99.96
2							0.0005	With a left side	0.0010	10	＜30	＞99.96
	3	0.0015	With a left side	0.0040	25	＜30							＞99.96
4							0.0020	With a left side	0.0040	30	＜30	＞99.96
	5	0.002	With a left side	0.0045	30	＜30							＞99.96
6							0.0030	With a left side	0.0055	40	＜30	＞99.96

Embodiment C-3 (the 2nd process)

By dissolving of phenol and acetone being reacted the obtain dihydroxyphenyl propane phenol that look is 50APHA and the mixture of impurity, accept multistage partial crystallization and handle, thereby separated out crystalline adduct.Then, thus the solution of this slip is made the crystalline adduct that filtration under diminished pressure obtains solid shape.Use the resulting refining phenol of method described later again, join the ratio of 2.5 weight unit according to adducts 1 weight unit and clean.In additive 20 ppm by weight of adding in the crystalline adduct (form and aspect: APHA is that 5-10, PH are below 5.05) that so obtains shown in table C-2, in temperature is 150 ℃, the concentration of oxygen is to dissolve processing under the condition of 0.0010vol% in the surrounding gas, and be evaporation process under the condition of 0.0010vol% to the concentration of the melt of acquisition like this oxygen in the pressure of 175 ℃ temperature, 10 holders and surrounding gas, after being removed fully, phenol just obtained dihydroxyphenyl propane.At this moment the amount of free phenol is below the 30wtppm.

Then, under conditions of air, when 175 ℃ temperature, 2 hours heating keeps to this dihydroxyphenyl propane do, heat stability test that Here it is (test A), the chien shih air is blown into when descending with 2 hours for 175 ℃ again, and this is called acceleration heat stability test (test B), afterwards, form and aspect are at this moment made an appraisal.Its result is illustrated in C-2.Yet test No.6-12 represents comparative example.

Table C-2

Experiment No	Additive	The form and aspect of the dihydroxyphenyl propane after the test
					Test A		Test B
		175℃-0hr	175℃-2hr	175℃-2hr
					1 2 3 4 5 6 7 8 9 10 11 12	Lactic acid oxalic acid glycerine sour lime tart apple acid ammonium oxalate magnesium phosphate terephalic acid ethylene glycol dimethyl oxalic acid hypophosphorous acid is received not have and is added	10 10 10 10 10 10-15 20 10-15 20-25 10-15 20-25 10-15	15 15 15 15 15 15 30 20 40 15-20 50 20	30 30 30 25 25 40 70 50-60 70-80 50 70 35-40

Yet the refining phenol that uses above is to dissolve the material of look as 6APHA." Combe, George Alexander that Ha-ス company produces draws special IR-118H+ resin under the contact conditions of 80 ℃ temperature and 50 minutes commercially available industrial phenol (moisture content concentration is 0.1wt%; impurity concentration is 0.05wt%) to be done contact and handles, thereby is that 175 ℃, tower top pressure are to obtain above-mentioned substance under the conditions of 560 holders in the base product temperature to adopt ロ-system ァ Application ト.

Comparative example C-4

With reference to Embodiment C-3, different is: adopt synthetic in addition dissolve look APHA at 5-10, pH in 4.85 crystalline adduct.Other is all the same with embodiment 3, tests.At this moment the form and aspect of the dihydroxyphenyl propane that is obtained are for shown in the table C-3.In addition, the concentration of free phenol is 50wtppm in the dihydroxyphenyl propane.

Table C-3

Experiment No	Additive	The form and aspect of the dihydroxyphenyl propane after the test (APHA)
					Test A		Experiment B
		175℃-0hr	175℃-2hr	175℃-2hr
					1 2 3	Oxysuccinic acid oxalic acid citric acid	20-25 20 20	30-35 25-30 20-25	60 50-55 55-60

Comparative example C-5

The base product temperature was 200 ℃ when being distilled except refining phenol, other was all identical with Embodiment C-3, thereby obtained dihydroxyphenyl propane.This material 175 ℃-0hr (hour) test A after the look that dissolves that shows be 30APHA.

Embodiment C-4 (the 3rd process)

That the reaction of phenol and acetone obtains by in the presence of acid catalyst, making, dissolve dihydroxyphenyl propane phenol that look is 50APHA and the mixture of impurity is accepted multistage partial crystallization, thereby obtain crystalline adduct (form and aspect: APHA5-10, pH4.85 are following).At the additive that adds in this crystalline adduct shown in table C-4, then, oxygen concn is to dissolve under the condition of 0.0010vol% in 150 ℃ temperature and surrounding gas, later on again 175 ℃ temperature, oxygen concn is under the condition of 0.0010vol% acquired melt to be made evaporation process in the pressure of 10 holders and the surrounding gas, and then removes phenol fully.At this moment, the amount of free phenol is 30wtppm.

Yet, again under air conditions, condition with the temperature (2 hours) of 175 ℃ temperature (0 hour) and 175 ℃ is made heat stability test (test A) to this dihydroxyphenyl propane, and 175 ℃ of acceleration heat stability tests (test B) that are blown into air down with 2.5 hours time intercropping, at this moment after form and aspect were judged, its result was shown in table C-4.Yet experiment NO6-9 is a comparative example.

In the additive shown in the table C-4, the addition of additive of the present invention (NO.1-5) be crystalline adduct middle strong acidity material in and a great deal of (is about 1ppm to crystalline adduct), with the addition of the additive of making comparisons (NO.6-8), be 20ppm for crystalline adduct.

Table C-4

Experiment No	Additive	The form and aspect (APHA) of test back dihydroxyphenyl propane
					Test A		Test B
		175℃-0hr	175℃-2hr	175℃-2hr
					1 2 3 4 5 6 7 8 9	Formic acid is received citric acid and is received malic acid and receive acetic acid and receive oxalic acid list ammonium malic acid oxalic acid citric acid and do not have interpolation	10～15 10～15 10～15 10～15 10～15 20～25 20 20 25	20 20 20 20 20 30～35 25～30 20～25 40～45	30～35 30～35 35～40 35～40 35～40 60 50～55 55～60 75

Embodiment C-5

With reference to Embodiment C-4, different is: using and dissolving look APHA5～10pH is 4.22 crystalline adduct.Other is all constant, thereby tests.Its result is shown in table C-5.

Yet, in the additive shown in the table C-5, in the magnesium citrate of invention and the addition crystalline adduct middle strong acidity material received of oxysuccinic acid and a great deal of (is about 4ppm for crystalline adduct), be used for the addition of the citric acid of comparison, be 20ppm for crystalline adduct.

Table C-5

Experiment No	Additive	The form and aspect of the dihydroxyphenyl propane after the test (APHA)
					Test A		Test B
		175℃-0hr	175℃-2hr	175℃-2hr
					1 2 3 4	The magnesium citrate oxysuccinic acid is received citric acid is not had interpolation	10～15 10～15 30 35	20 25 60 75	30～35 35～40 75 90

Embodiment C-6 (the 4th process)

As the indirect heating formula encloses container that is to use the SUS304 system that dissolves device, as the desorption apparatus that is to use the SUS304 system of evaporation unit.The crystalline adduct supply-pipe has been set up on the top that dissolves device, in addition, has set up the dissolution liquid pipe arrangement in its bottom, this dissolution liquid pipe arrangement is connected the middle portion of desorption apparatus.In addition, be provided with the pipe arrangement that phenol steam is discharged usefulness on the top of this desorption apparatus, be provided with the pipe arrangement that the dihydroxyphenyl propane dissolution liquid is discharged usefulness in its bottom.Yet above-mentioned pipe arrangement is the SUS304 system.

Then, in the above-mentioned device series that constitutes, to dissolving the inner-wall surface of device, the inner-wall surface of desorption apparatus, dissolve the pipe arrangement between device and the desorption apparatus, be attached to the discharge pipe arrangement of the dihydroxyphenyl propane dissolution liquid in the desorption apparatus, clean its inwall in such a way.

(1) dissolves the cleaning of device inner-wall surface

Under normal pressure, spray inner-wall surface by nozzle with 130 ℃ phenol liquid, spray again after doing fully to clean 150 ℃ phenol/dihydroxyphenyl propane mixed solution (blend gravity is: 65/35) thus inner-wall surface is done to clean fully.

(2) cleaning of desorption apparatus inwall

Under normal pressure, 130 ℃ phenol is flowed out from the nozzle that is attached to this device top, centre portions in installing is cleaned.And then then use phenol/dihydroxyphenyl propane mixture (the mixed weight ratio is 65/35) of 150 ℃ to circulate again with 130 ℃ phenol, so that the device inner-wall surface is fully got wet.Then, under the conditions of 180 ℃ and 10 holders, circulate the again mixture (the blended weight ratio is 65/35) of phenol/dihydroxyphenyl propane.

(3) cleaning of pipe arrangement inwall

Thereby 130 ℃ phenol circulation is cleaned through in the pipe arrangement.At this moment, noted not making the inner-wall surface of pipeline to have gas phase.

Yet by confirming after the above-mentioned cleaning: at each device and the accompanying oxygen of pipe arrangement inner-wall surface is 1m ²Inner-wall surface below 5 mmoles.

Then, as described above, adopted the device of the dissolution liquid contact of dissolution liquid that crystalline adduct is arranged and dihydroxyphenyl propane, and the inner-wall surface of pipe arrangement has been made the device series that deoxygenation is handled in advance, so just can from the refining crystallization adducts of making as follows (dissolving look APHA is 5), remove phenol, thereby isolate dihydroxyphenyl propane through evaporation.

(manufacturing of crystalline adduct)

Thereby accepting partial crystallization by the mixture that dissolves dihydroxyphenyl propane, phenol and impurity that look is 50APHA that phenol and acetone is reacted obtain handles and separates out adducts.This slip is made filtration under diminished pressure, and the refining phenol that obtains with the aftermentioned method is used the ratio of 2.5 weight unit and is cleaned this refining phenol with adducts 1 weight unit again, thereby obtains the refining crystallization adducts.

(manufacturing of refining phenol)

The above-mentioned refining phenol that uses is to dissolve the material of look as 6APHA, and it makes by the following method.The Combe, George Alexander made from ロ-system ア Application De Ha-ス company draws special IR-118H+ resin, (moisture concentration is 0.1wt% to commercially available phenol under the duration of contact of 80 ℃ temperature and 50 minutes, impurity concentration is 0.05wt%) contact processing, it is 175 ℃ in the base product temperature then, tower top pressure is under the conditions of 560 holders acquired handled thing to be implemented distillation, thus from recovered overhead refining phenol.

(operational condition)

The above-mentioned operational condition that dissolves device and desorption apparatus is as follows:

(dissolving device)

Temperature: 130 ℃

Pressure: normal pressure

The concentration of oxygen: 0.0005vol% in the surrounding gas

(desorption apparatus)

Temperature: 175 ℃

Pressure: 10 holders

The concentration dividing potential drop of oxygen: 0.0015vol% in the surrounding gas

Comparative example C-6

With reference to Embodiment C-6.Except each inwall that dissolves device, desorption apparatus and pipe arrangement not being done the clean, all the other are all the same with Embodiment C-6, thereby test.

The dissolve look of the dihydroxyphenyl propane that obtains in the foregoing description C-6 and comparative example C-6 in the time of 175 ℃ is indicated on following table.

(table C-6)

Numbering	Dihydroxyphenyl propane dissolve look (APHA)
		Embodiment C-6	10
Comparative example C-6	80

Embodiment C-7 (the 5th process)

As the crystallization dissolver, used the indirect heating formula encloses container of SUS316 system, as the evaporating of crystalline adduct dissolution liquid, used portion within it to be filled with 2 packing towers of SUS304 system of the filler of SUS316 system.

Dissolve device, set up the crystalline adduct supply-pipe at an upper portion thereof, set up the dissolution liquid pipe arrangement, this pipe arrangement is connected the centre of the 1st packing tower in its bottom.In the 1st packing tower, set up the discharge pipe arrangement of phenol steam at its top, and the bottom sets up the dissolution liquid pipe arrangement that contains dihydroxyphenyl propane and phenol, this pipe arrangement is connected the centre of the 2nd packing tower.The top of tower of the 2nd packing tower has been set up the mixing steam discharge that contains phenol, steam and a small amount of dihydroxyphenyl propane and has been joined with pipe, this pipe arrangement is connected in the condensing works shown in Figure 2, in addition, in the bottom of the 2nd packing tower, set up the vent pipe and the steam suppling tube of dihydroxyphenyl propane.

Yet, disposed the heating coil of the heating steam of circulating in each bottom of aforementioned the 1st packing tower and the 2nd packing tower.In addition, above-mentioned each pipe arrangement is the product of SUS316 system.

In by the above-mentioned device series that constitutes, this is dissolved the inner-wall surface of device, the inner-wall surface of the 1st packing tower and the 2nd packing tower and filling surface, dissolve the pipe arrangement between device and the 1st packing tower, the dihydroxyphenyl propane vent pipe that is arranged on the pipe arrangement between the 1st packing tower and the 2nd packing tower and is arranged on the 2nd packing tower bottom, thus all be to implement clean according to following way to remove accompanying oxygen.

(1) dissolves the cleaning of device inner-wall surface

By nozzle, the inside phenol of 130 ℃ of wall jet under non-pressurized condition, to inner-wall surface do fully peace and quiet after, spray the mixture (the mixed weight ratio is 65/35) of phenol/dihydroxyphenyl propane of 150 ℃ again, thereby inner-wall surface done to clean fully.

(2) to the cleaning of packing tower inner-wall surface and filling surface

Under normal pressure, 130 ℃ phenol is flowed into from the nozzle that is attached to this device top, thereby the inside of device is cleaned.And then then circulate, thereby device wall and filling surface are fully got wet with phenol/dihydroxyphenyl propane mixture (mixed weight compares=65/35) of 150 ℃ with 130 ℃ phenol.Then, again under the conditions of 180 ℃ and 10 holders, the mixture (mixed weight than=65/35) of circulation phenol/dihydroxyphenyl propane.

(3) cleaning of pipe arrangement inner-wall surface

Thereby the phenol that makes 130 ℃ circulates in pipe arrangement and realizes cleaning.At this moment paying close attention to not make has gas phase to exist on the inside pipe wall face.

Yet, according to aforesaid cleaning, in the amount that dissolves the accompanying oxygen of the inner-wall surface of device, packing tower inner-wall surface and filling surface be: 1m ²Surface-area be 5 mmoles.

Then, dissolve device, packing tower and pipe arrangement surface in the contact of the dissolution liquid of dissolution liquid that crystalline adduct is arranged and dihydroxyphenyl propane have been made the aforementioned means that deoxygenation handles in advance and are obtained using, from the refining crystallization adducts (dissolving look APHA:5) that makes by the following method, remove phenol through evaporation, thereby Separation and Recovery goes out dihydroxyphenyl propane, meanwhile, the mixed vapour that derives from the 2nd packing tower top being made cooling condensation handles.

(manufacturing of crystalline adduct)

Be subjected to partial crystallization by the mixture that dissolves dihydroxyphenyl propane, phenol and impurity that look is 50APHA that phenol and acetone is reacted obtain and handle, thereby separate out crystalline adduct.Then this solution is made filtration under diminished pressure and handle, so obtain the crystalline adduct of solid shape.The refining phenol that obtains with the aftermentioned method is joined the ratio of 2.5 weight unit this is cleaned with adducts 1 weight unit then, thereby obtains the refining crystallization adducts.

(manufacturing of refining phenol)

Above-mentioned employed refining phenol is to dissolve the material that look is 6PHA, and it is to make with following method.The Combe, George Alexander made from ロ-system ァ Application De Ha-ス company draws special IR-118+ resin, under the duration of contact of 80 ℃ temperature and 50 minutes commercially available phenol (moisture concentration is 0.1wt%, and impurity concentration is 0.05wt%) is done contact and handles, thereby obtain handled thing.Be 175 ℃ in the base product temperature again then, tower top pressure is under 560 conditions of holding in the palm acquired above-mentioned handled thing to be distilled, thereby is recovered to refining phenol from the distillation cat head.

(operational condition)

The above-mentioned device that dissolves, the operational condition of the 1st packing tower, the 2nd packing tower and cooling condensation device series be following shown in.

(dissolving device)

Temperature: 130 ℃

Pressure: normal pressure

The concentration of oxygen is in the surrounding gas: 0.0005vol%

(the 1st packing tower)

Temperature: 170 ℃

Pressure: 10 holders

The concentration of oxygen: 0.0015vol% in the steam condition

(the 2nd packing tower)

Temperature: 180 ℃

Pressure: 10 holders

The feed rate of steam: the 1kg dissolution liquid is 0.08kg

The concentration of oxygen: 0.0002vol% in the steam condition

(operational condition of the 1st water cooler of Fig. 6)

(1) is directed into the parsing gas of the 1st water cooler 1 from pipeline 3

Pressure: 10 holders

Temperature: 180 ℃

Form: dihydroxyphenyl propane is 25wt%, and phenol is 25wt%, and steam is 50wt%

(2) the 1st heat-eliminating medium (phenol) that imports from pipeline 5

Temperature: 50 ℃

The weight ratio of heat-eliminating medium/stripping gas: 6

(3) from the rate of recovery of the dihydroxyphenyl propane of desorption gas in the water cooler 1: 100%

(operational condition of the 2nd water cooler of Fig. 6)

(1) imports the uncondensed gas of the 2nd water cooler from pipeline 8

Pressure: 10 holders

Temperature: 51 ℃

Form: phenol 65wt%, steam 35wt%

(2) be directed into the 2nd heat-eliminating medium (the phenol aqueous solution) of the 2nd water cooler 2 from pipeline 9

Temperature: 9 ℃

The weight ratio of heat-eliminating medium/uncooled gas: 190

(3) each rate of recovery of phenol that uncondensed gas obtains from water cooler 2 and steam.

The rate of recovery of phenol: 100%

The rate of recovery of steam: 100%

Embodiment C-8

With reference to Embodiment C-7, except only the inner-wall surface of each packing tower and the surface of filler being implemented the deoxygenation processing, all the other are all the same with embodiment 7, thereby test.

Comparative example C-7

With reference to Embodiment C-7, except not carrying out the deoxygenation processing fully, other is all the same with embodiment 7, thereby tests.

More than the dihydroxyphenyl propane that obtains in each embodiment and the comparative example in the time of 175 ℃, dissolve colour specification in following table.

Table C-7

Numbering	Dihydroxyphenyl propane dissolve look (APHA)
		After dissolving at once
	Embodiment C-1		10
Embodiment C-2		15
	Comparative example C-1		200
Comparative example C-2		200

Embodiment C-9 (the 6th process)

The reaction mixture that phenol and acetone is reacted and obtain is handled by the multistage partial crystallization and is obtained, adopting refining phenol that it is dissolved look APHA then is that this crystalline adduct of 5 dihydroxyphenyl propane phenol is carried out the part dilution, in the time of 130 ℃, heat again, thereby become the phenol solution that contains dihydroxyphenyl propane 30 heavy %.

As stock liquid, adopt this phenol solution evaporation unit shown in Figure 6 to handle.

Then, the composition to the main operating condition of device shown in Figure 6 and the liquid by main conduit line is expressed as follows.

(1) the 1st vaporizer 1

(i) temperature of external heater: 170 ℃

(ii) internal pressure: 20 holders

(2) the 2nd vaporizers 2

(i) indirect heating actuator temperature: 180 ℃

(ii) internal pressure: 10 holders

(3) the 3rd vaporizers 3

(i) indirect heating actuator temperature: 180 ℃

(ii) internal pressure: 10 holders

(4) by the phenol containing ratio in the dihydroxyphenyl propane of pipeline 12 be: 2.7 weight %

(5) dihydroxyphenyl propane by pipeline 16

(i) containing ratio of phenol: 23wtppm

(ii) dissolving look: APHA is 20

(6) feed rate of the steam by pipeline 15: the dihydroxyphenyl propane by pipeline 14 is that 1 weight unit is 0.04 weight unit.

Comparative example C-9

The operating condition of the 1st vaporizer 1 is set at 190 ℃, 10 whens holder, and the containing ratio by the phenol in the dihydroxyphenyl propane of pipeline 12 can only be reduced to 7 weight %, therefore, just causes the running instability of the 1st vaporizer.

Comparative example C-10

When making each indirect heating temperature of the 2nd vaporizer 2 and the 3rd vaporizer 3 be set at 200 ℃, the look that dissolves of the product dihydroxyphenyl propane by pipeline 16 just becomes 45, and the containing ratio of phenol is 70ppm just.

Embodiment C-10 (the 7th process)

The reaction mixture that phenol and acetone is reacted and obtain, obtain by multistage partial crystallization processing, be that the dihydroxyphenyl propane phenol crystal adduct of 5APHA partly dilutes with refining phenol to being in (pH is 5.05) under the neutrallty condition in fact, dissolving look then, just having obtained content of bisphenol A after heating under 130 ℃ is the phenol solution of 30 weight %.

With the stock liquid of this phenol solution, adopting evaporation unit shown in Figure 6 is that example is handled.

Composition to the main operating condition of the device series shown in Fig. 6 and the liquid component by main conduit line is expressed as follows.

(1) the 1st vaporizer 1

(i) indirect heating actuator temperature: 170 ℃

(ii) internal pressure: 20 holders

The (iii) concentration of oxygen: 0.0010vol% in the surrounding gas

(2) the 2nd vaporizers 2

(i) indirect heating actuator temperature: 180 ℃

(ii) internal pressure: 10 holders

The (iii) concentration of oxygen: 0.0030vol% in the surrounding gas

(3) the 3rd vaporizers 3

(i) indirect heating actuator temperature: 180 ℃

(ii) internal pressure: 10 holders

The (iii) concentration of oxygen: 0.0030vol% in the surrounding gas

(4) dihydroxyphenyl propane by pipeline 16

(i) phenol containing ratio: 29wtppm

(ii) dissolve look: APHA15

(5) feed rate of the steam by pipeline 15: the dihydroxyphenyl propane by pipeline 14 is 0.04 weight unit when being 1 weight unit.

Embodiment C-11

With reference to Embodiment C-10, in the phenol solution that contains as the dihydroxyphenyl propane of raw material, add the additive 20wtppm shown in the table 8, other is all identical with Embodiment C-10, thereby tests.Obtained highly purified dihydroxyphenyl propane (APHA:10, the containing ratio of phenol are 27wtppm) through this experiment and by pipeline 16.

Then, under the temperature of conditions of air and 175 ℃, change last 2 hour, this dihydroxyphenyl propane is heated maintenance, this is heat stability test (test A), again at 175 ℃ and change and be blown into air last 2 hour, thus the heat stability test of acceleration.Evaluation result at this moment form and aspect is listed in table C-8.

(table C-8)

Experiment No	Additive	The form and aspect of the dihydroxyphenyl propane after the test (APHA)
					Test A		Test B
		175℃-0hr	175℃-2hr	175℃-2hr
					1 2 3 4 5	The acid of lactic acid oxalic acid glycerol sour lime crab apple	10 10 10 10 10	15 15 15 15 15	30 30 30 25 25

Embodiment C-12

Accept the multistage partial crystallization by the mixture that phenol and ketone is reacted obtain, dissolve dihydroxyphenyl propane, phenol and impurity that look is 50APHA and handle, thereby separate out crystalline adduct.Then this slurry solution is made filtration under diminished pressure, thereby obtain solid shape crystalline adduct.Then,, join the ratio of 2.5 weight unit with the adducts of 1 weight unit and clean, thereby obtain crystalline adduct (form and aspect: APHA5～10, pH is below 5.05) with the refining phenol that the aftermentioned method obtains.

Then, in this crystalline adduct 1 weight unit, add refining phenol 1 weight unit, under 130 ℃ temperature, dissolve processing, according to the method identical the melt (pH5.05) of gained is made evaporation process then, thereby obtain highly purified dihydroxyphenyl propane (purity is at 99.96wt%) with Embodiment C-1.The phenol content of this dihydroxyphenyl propane is below the 30wtppm, and in addition, it dissolves look is 15APHA.

Yet, the refining phenol of above-mentioned use is the material that dissolves look 6APHA, (moisture concentration is 0.1wt% to commercially available industrial phenol, impurity concentration is 0.05wt%), the Combe, George Alexander made from ロ-system ァ Application De Ha-ス company draws special IR-118H+ resin, under 80 ℃ temperature, do 50 minutes contact and handle, be that 175 ℃, tower top pressure are to distill processing under the conditions of 560 holders in the base product temperature again, thereby obtained above-mentioned substance.

Embodiment C-13

According to flow process shown in Figure 7, carried out the continuous condensation process of stripping gas, the 1st water cooler 1 at this moment and the operational condition of the 2nd water cooler 2 are as follows.

(operational condition of the 1st water cooler)

(1) is directed into the desorption gas of the 1st water cooler 21 from pipeline 23.

Pressure: 10 holders

Temperature: 180 ℃

Form: dihydroxyphenyl propane is 25wt%, and phenol is 25w%, and steam is 50wt%

(2) the 1st heat-eliminating medium (phenol) that imports from pipeline 25

Temperature: 50 ℃

The weight ratio of heat-eliminating medium/stripping gas: 6

(3) from the rate of recovery of the dihydroxyphenyl propane of the stripping gas of water cooler 21: 100% (operational condition of the 2nd water cooler)

(1) is directed into the uncondensed gas of the 2nd water cooler from pipeline 28.

Pressure: 10 holders

Temperature: 51 ℃

Form: phenol is 65wt%, and steam is 35wt%

(2) be directed into the 2nd heat-eliminating medium (aqueous solution of phenol) of the 2nd water cooler 22 from pipeline 29

Temperature: 9 ℃

The weight ratio of heat-eliminating medium/uncondensed gas: 190

(3) each rate of recovery of the phenol of the uncondensed gas in water cooler 21 and steam.

The rate of recovery of phenol: 100%

The rate of recovery of steam: 100%

(simple declaration of drawing)

(Fig. 1)

Represented example for the plant system drawing of the 1st process of the present invention of making crystalline compounds.

(nomenclature)

A, B, C, D partial crystallization tower

The E equipment for separating liquid from solid

F crystalline adduct dissolving tank

The P inner core

Q micro-crystallization adducts dissolving vessel

(Fig. 2)

Represented to make example of plant system drawing of the 2nd process of the present invention of crystalline adduct.

(nomenclature)

A, B partial crystallization tower

The P inner core

The dissolving vessel of Q micro-crystallization adducts

(Fig. 3)

Represented example for the plant system drawing of the 3rd process of the present invention of making crystalline adduct.

(nomenclature)

1 urceolus

2 inner cores

3 micro-crystallization adducts dissolving vessels

A partial crystallization tower

(Fig. 4)

Represented example for the plant system drawing of the present invention's the 4th process of making crystalline adduct.

(nomenclature)

A the 1st partial crystallization tower

B the 2nd partial crystallization tower

3-4 first water cooler commonly used

5 standby water coolers

6-7 the 2nd water cooler commonly used

The 8-13 pump

101-107 partial crystallization liquid is transferred pipeline

(Fig. 5)

Expression is for the example of one of flow process of the 5th process of the present invention of making crystalline adduct.

(explanation of symbol)

A-1, A-2, A-3 partial crystallization operation

B-1, B-2, B-3 solid-liquid separation process

C-1, C-2 be dissolution process again

(Fig. 6)

The example of having represented one of the plant system drawing the when phenol solution that contains dihydroxyphenyl propane done desorb and handle.

(nomenclature)

1,2,3 thin-film evaporators

4 external heaters

(Fig. 7)

The example of having represented one of plant system drawing for the condensation stripping gas.

(nomenclature)

21 the 1st water coolers

22 the 2nd water coolers

(Fig. 8)

Expression is for other example of the plant system drawing of condensation stripping gas.

(nomenclature)

21 the 1st water coolers

22 the 2nd water coolers

41 water coolers

45 dividing plates

Claims (3)

1. the manufacture method of a dihydroxyphenyl propane phenol crystal adduct, described method is, be ready to partial crystallization tower and water cooler, emit a part of crystalline adduct slip from this partial crystallization tower, and cool off with this water cooler, by making cooled crystalline adduct slurry recycle, crystalline adduct is separated out in this partial crystallization tower to this partial crystallization tower, the method that the crystalline adduct of separating out is emitted and separated from the crystalline adduct slip from this partial crystallization tower

Described method is characterised in that:

Be set up in parallel 2-3 above-mentioned water cooler, fixed 1 is standby water cooler in 2-3 water cooler, only uses standby water cooler water cooler in addition that the crystalline adduct slip is cooled off,

Make and to have separated out water cooler and standby water cooler crystalline adduct, that heat transfer efficiency has descended at heat-transfer surface and exchange, thereby carry out operate continuously,

Meanwhile, the regeneration of the water cooler that heat transfer efficiency has descended by being attached to other setting, makes the crystalline adduct dissolving of paying on heat-transfer surface, thereby makes this water cooler regeneration to heat with the circulation line of the medium of heating.

2. method according to claim 1 is characterized in that:

The said products crystalline adduct slip is carried out filtration treatment, in this crystalline adduct, make the part of particle diameter in 100 μ m or following micro-crystallization adducts to filtering side shifting, thus reclaim particle diameter at 100 μ m or following micro-crystallization adducts proportion in 20 weight % or following thick crystalline adduct.

3. device that is used for the preparation method of claim 1, its constitutional features is:

This device has partial crystallization tower and 2-3 water cooler, and 1 in 2-3 water cooler as standby water cooler,

This partial crystallization tower enters the mouth in the loopback that its sidewall locations is provided with the crystalline adduct slip, is provided with the outlet of crystalline adduct slip in its bottom, and each water cooler is respectively equipped with entrance and exit,

Between the inlet of the outlet of the crystalline adduct pulp flow of partial crystallization tower and each water cooler and enter the mouth between the outlet with each water cooler respectively in the loopback of crystalline adduct slip that the handover means with the crystalline adduct slip are connected,

The formation configuration of described device is as follows, can make the crystalline adduct slip optionally pass through the water cooler beyond any this 2-3 water cooler, and be transferred to the loopback inlet of the crystalline adduct slip of this partial crystallization tower from the crystalline adduct pulp flow outlet of this partial crystallization tower.

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