CN108794522A - A kind of tricresyl phosphate（The chloro- 2- propyl of 1-）The Total continuity stream production technology of ester - Google Patents

Abstract

The present invention relates to a kind of tricresyl phosphates（The chloro- 2- propyl of 1-）The finished product and Total continuity stream production technology of ester.By the stage of reaction and post-processing stages, technique carries out the present invention continuously, incessantly as a whole, raw material phosphorus oxychloride, propylene oxide and catalyst continuously enter reactor feed mouth, and the tricresyl phosphate for meeting commercial standard is continuously obtained in reactor outlet（The chloro- 2- propyl of 1-）Ester finished product realizes and quickly prepares high quality tricresyl phosphate（The chloro- 2- propyl of 1-）Ester（TCPP）Finished product.The Total continuity stream production technology of the present invention not only realizes efficiently production, high quality product and stable storing, TCPP finished products without aldehyde type impurities, not sour regurgitation, be free of the corresponding metal cation of catalyst, and the wastewater flow rate of technique generation is few, phosphorus content is low, it is good for the environment, and is suitble to security industry metaplasia production.

Description

A kind of Total continuity stream production technology of tricresyl phosphate (the chloro- 2- propyl of 1-) ester

Technical field

The present invention relates to chemical classes additive flame retardant fields, and in particular to a kind of to prepare tricresyl phosphate (the chloro- 2- propyl of 1-) The continuous flow production technology of ester (TCPP) finished product.

Background technology

Tricresyl phosphate (the chloro- 2- propyl of 1-) ester is also three-(2- chloro isopropyls) phosphates, tricresyl phosphate chloropropyl ester etc., abbreviation TCPP is a kind of phosphorus system additive flame retardant, and flame retardant effect is notable, is widely used in polyurethane soft foamed plastics, hard Foamed plastics, epoxy resin, the multiple polymers material such as phenolic resin.

The production process of TCPP includes mainly the stage of reaction and post-processing stages, and simplified process is as follows：

Well known to those skilled in the art, the industrial process for preparing TCPP is as follows at present：It, will under the conditions of anhydrous and oxygen-free Catalyst is dissolved in raw material phosphorus oxychloride (POCl₃) in, propylene oxide (PO) is slowly added dropwise at 40~60 DEG C, causes in reaction Afterwards, controlling reaction temperature continues that propylene oxide is added dropwise at 55~60 DEG C, keeps the temperature a few hours after being added dropwise to complete, keeps reaction all complete At then sloughing remaining propylene oxide under vacuum, obtain TCPP crude products.Crude product is added in lye again, 60~ 90 DEG C carry out alkali cleaning to crude product, make oil phase to be washed with water to neutrality again after stratification, will be oily after stratification It is mutually placed under vacuum condition and sloughs remaining moisture, the TCPP finished products for meeting commercial standard can be obtained.In the stage of reaction slowly Propylene oxide and reaction soaking time is added dropwise in total ten to more than tens of hours, in post-processing stages alkali cleaning, washing include It repeatedly stirs and washing total time is more than a few hours, along with the vacuum after the completion of reaction except PO is operated, the dehydration after washing The operations such as dry, the time that entire production process needs are very long.And the raw material propylene oxide (PO) that reaction uses, boiling point It is 34.24 DEG C, volatile, it is less than the well-defined reaction temp of phosphorus oxychloride and propylene oxide, and easy open loop is poly- under the action of catalyst It closes, discharges amount of heat, explosion limit is 3.1~27.5% (VOL), is an inflammable, explosive, dangerous, toxic chemistry examination Agent；Raw material phosphorus oxychloride is a kind of water white transparency industrial chemicals, and strong smoke has hygroscopicity, there is very strong corrosive, meets water, alcohol Equal substances very exothermic, has very high reactivity.Both raw materials will discharge a large amount of heat in reaction Contact, gently Then temperature runaway generates impurity, seriously can then make reaction solution coking, or even explosion accident occurs.So current production technology be all Under strong heat exchange, lower temperature conditions, the heat that propylene oxide is slowly dropped in phosphorus oxychloride, and is in time generated reaction moves Remove, time for adding and soaking time after being added dropwise to complete respectively will a few hours, so TCPP production technologies are to heat transfer efficiency meeting There is very high requirement.Since in process of production, the complete raw material of unreacted largely stops in a device, if there is leakage (such as Condensed water is penetrated into after reactor aging), the liquid of highly acid may escape, and have very high security risk.Dropwise operation with Material dropping or speed and the uninterrupted that consersion unit is added do not have a direct relationship, the dropwise addition, and most apparent one A feature is any time during dropwise addition, and at least a kind of reaction raw materials (for example, propylene oxide) are insufficient amount of, are needed Can be reached after dropwise addition after a period of time makes each reactant in reaction reach enough.For example, Chinese patent It is mentioned in the embodiment 1 of CN106565773A, 5000L reaction kettles, last consignment of material is kept on file 600kg, and the trichlorine oxygen of 2600kg is put into Phosphorus, is added the phosphorus trichloride of 5kg, the pyrophosphoryl chloride of 6kg, after the alchlor of 7kg, then logical propylene oxide, temperature is at 35-40 DEG C Flow control is in 50-100kg/h (initial reaction stage)；Temperature is at 45-50 DEG C, and flow control is in 100-300kg/h (reaction mid-term)； Temperature is at 50-55 DEG C, and flow control is in 300-400kg/h (reaction later stage).Although the addition of propylene oxide in process of production It is held under higher flow, but entire adition process oxypropylene is that segmentation is added, and belongs to the mode of dropwise addition.

Using existing industrialized production process, the TCPP finished products for meeting commercial standard obtained by post-processing stages are very It is susceptible to the higher situation of unstable product quality, impurity content.Particularly, the acid value (acid value) of TCPP finished products Can change during storage, transport or downstream user use, cause final product quality unstable, and final product quality and Purity has apparent fluctuation, wherein most important index is containing for acid value (acid value) in TCPP finished products and aldehyde type impurities Amount, aldehyde type impurities is again with 2- methyl alkene valeral contents for main judging quota.Acid value refers to complete in 1 gram of TCPP finished product for neutralizing The milligram number of the required potassium hydroxide of portion's acidic components (KOH), can be indicated with mgKOH/g, embody be the TCPP at The number of product acidic substance content.Acid value is bigger, and the risk used downstream is bigger, can reduce the product matter of downstream product Amount, it is serious to cause downstream product production failure.The TCPP finished products of prior art production are in storage, transport or downstream user It can slowly be hydrolyzed during use, generate acidic materials, which has the function of self-catalysis, and acid value is caused to accelerate to increase, The phenomenon that this acid value increases referred to as sour regurgitation.Sour regurgitation degree is higher, illustrates that the stability of TCPP finished products is poorer.Sour regurgitation phenomenon goes out There is a prodigious threat referring now to the use of TCPP, but the equal nothing of TCPP finished products obtained by current production technology and the prior art Method avoids this problem of sour regurgitation.Since this problem can not avoid at present, downstream manufacturers also have to receive and using micro anti- The TCPP finished products of acid can only overcome sour regurgitation by shortening TCPP storage times and adjusting itself production formula with technique Caused by adversely affect, actually cause inconvenience and hidden danger to downstream client.Even if having prepared the TCPP of low acid value Finished product, but during storage, transport or downstream user use, still inevitably sour regurgitation phenomenon.Wherein, In order to it is simple and quick detect TCPP finished products whether sour regurgitation and sour regurgitation degree, can by using senile experiment method into Row characterization and embodiment, the specific method is as follows：It takes in 60g samples to the aging bottle of 60ml volumes, constant temperature 100 is put into after being sealed DEG C baking oven in keep the temperature 3h, front and back comparison acid value variation.The acid value of product is finished product acid value before aging, the acid of product after aging Value is acid value after aging, and the difference or ratio after aging between acid value and finished product acid value can embody sour regurgitation degree：Difference is bigger, Sour regurgitation degree is higher, and product stability is poorer, and product quality is lower, and correspondingly, difference is small, illustrates that the extent of reaction is lower, product Stability higher, product quality is also with regard to higher；Or ratio is bigger, sour regurgitation degree is higher, and product stability is poorer, product quality Lower, correspondingly, ratio illustrates that the extent of reaction is lower closer to 1, and product stability higher, product quality is also with regard to higher.

The catalyst that the stage of reaction of TCPP uses is usually lewis acid catalyst or corresponding Exemplary Lewis Acid ionic liquid Body catalyst, for example, the catalyst is selected from alchlor, titanium tetrachloride, positive four butyl ester of metatitanic acid, zinc chloride, magnesium chloride, chlorination It is one or more in iron or corresponding ionic-liquid catalyst.After the stage of reaction, need to remove by post-processing stages Remaining catalyst.Post-processing stages can remove most catalyst using lye, but can not completely remove catalyst correspondence Metal cation (for example, catalyst be AlCl₃, corresponding metal cation is Al³⁺), the metal cation it is residual Allowance be usually it is tens of arrive hundreds of ppm, and the presence of the metal cation can influence the stability of TCPP finished products, especially When there are the remaining TCPP finished products of metal cation, when being contacted with the active material (for example, hydrone in air) containing proton, lead TCPP finished products are caused to be very easy to sour regurgitation.

Aldehyde type impurities mainly since the production process time is long, lead in production process phosphorus oxychloride oxidation propylene oxide and It generates, 2- methyl alkene valeral therein has special stench, cannot be thoroughly removed by post-processing stages, can be by sensitive gas Taste is brought into downstream takeaway, severely impacts the quality of downstream product, therefore industrial production requires the content of the aldehyde, Current production technology can generally have the residual of 100-200ppm, have part to be reported in TCPP after conventional post-processing, then By additional oxidation, the operation of the further work-ups such as additive is added, aldehyde type impurities can be made to be reduced to 10ppm or so, but existing Some aftertreatment technologies can not thoroughly remove aldehyde type impurities, still can be had some impact on to downstream product.In addition, the prior art The residual for reducing aldehyde type impurities is can only to reduce residual quantity, but can not be made without aldehyde type impurities by multiple purification steps TCPP finished products, it is even more impossible to directly produce the TCPP finished products without aldehyde type impurities, it is necessary to could be real by more purification steps The purpose of aldehyde value is now reduced, and aldehyde type impurities cannot be removed completely, which again increases time costs and processing cost.

The requirement of TCPP finished products for meeting commercial standard at present is：Acid value (mg KOH/g)≤0.1, moisture content (wt.%)≤ 0.1, color and luster (APHA)≤50, but the prior art can not prepare that acid value stablizes (not sour regurgitation), the content of aldehyde material is 0 (no Aldehyde-containing type substance) and without the TCPP finished products of the corresponding metal cation of catalyst (content of the metal cation is 0).

Meet the TCPP finished products of commercial standard in order to obtain, after the stage of reaction, needs after being carried out to TCPP crude products It handles.Aftertreatment technology industrial at present obtains the low finished product of acid value using the washing process that first alkali cleaning is washed again, also has The technique less finished product of quality higher, impurity in order to obtain, can increase by a step acid cleaning process before alkali cleaning.Due to TCPP finished products All unstable, the facile hydrolysis in highly acid and the aqueous solution of strong basicity, in order not to reduce yield, whether pickling or alkali cleaning, The concentration of the bronsted lowry acids and bases bronsted lowry used cannot be too high, but is to ensure washing effect, and the dosage of acid solution and aqueous slkali is not small, together The water that Shi Shuixi is used is also big, and it is high to directly contribute the waste water that is produced in production process, and cost for wastewater treatment is also therewith It greatly promotes, these are all well known to those skilled in the art.Also, since the time of post-processing is longer, cause TCPP in alkali Property environment under decompose so that post-processing Phosphorus From Wastewater content it is higher, usually, the organophosphor all in 2000ppm or more, waste water Content controls in environmental protection to be strict, and discharge standard is only 8ppm, it is necessary to be handled accordingly, reach discharge mark It can be discharged after standard, this also significantly enhances production cost, and current production technology can not significantly reduce water consumption and wash The organic phosphorous content in rear water is washed, this directly leads to the increase of production cost, reduces the productivity effect of finished product.

And industrial TCPP production technologies are still carried out using traditional mode of production from post-processing is reacted at present, especially It is the stage of reaction, using propylene oxide is slowly added dropwise.Meanwhile current TCPP production technologies have used traditional reaction to set Standby (such as reaction kettle, reactor, cascade system reactor, dispenser, reaction tower etc. with stirring), there is multiple stop in centre And waiting, this all to need the long period that could complete entire production process, this can lead to the unstable of final product quality, have Apparent fluctuation, such as acid value size, aldehyde type impurities content and metal cation residual quantity.Although existing TCPP continuous productions at present The report of technique, but the TCPP continuous production processes currently reported also have prodigious distance in terms of realizing industrialization, either There is its fatal defect.

TCPP production technologies refer to that raw material obtains TCPP crude products, TCPP crude products post-treated stage by the stage of reaction Obtain the process of the high-quality high commercially available TCPP finished products of purity.Production technology includes the work of the stage of reaction and post-processing stages Skill, by two operation stages, technique considers as a whole.Each technical process of production technology has specific technique Parameter, such as time, temperature, pressure, complete all production processes to be known as production technology total time total time (including anti- Answer the time in stage and the time of post-processing stages).Production technology total time can directly comment the efficiency of production technology Valence, i.e. production technology total time are shorter, and production technology efficiency is higher.In including the technique of multistep reaction or operating procedure, If wherein certain several step is continuous or only simply connects each step in original batch technology, centre warp The technique for going through the production processes such as stop, waiting, the technique are still discontinuous flow production technology, are typically used Stirring slurry, reaction kettle or consecutive reaction kettle, reactor, cascade system reactor, dispenser, reaction tower etc. with stirring are traditional Chemical production equipment, another intuitive performance is comparatively all comparing production technology total time for discontinuous flow production technology Long, usually in a few hours, ten a few houres, tens of hours, a other reaction even up to several days, this can reduce entire technique Production efficiency also brings along certain security risks.And only all steps are all continuous and material is in entire technical process In continuously flow, do not stop waiting, the entire technical process includes the technique of the stage of reaction and post-processing stages, It is continuously added to raw material, continuous reacted stage and post-processing stages are continuously available the product for meeting commercial standard, could be known as Total continuity stream production technology (or whole process continuous processing), that is, the stage of reaction and post-processing stages are not stopped or are waited It waits for.The production technology of TCPP, the technique for including the stage of reaction and post-processing stages, by two operation stages work as a whole Skill considers；The continuous flow production technology of TCPP refers to that technique is continuous as a whole by the stage of reaction and post-processing stages Ground carries out incessantly, and raw material continuously enters reactor feed mouth, is continuously met in reactor outlet The TCPP finished products of commercial standard.The production technology total time of TCPP, include the total time of the stage of reaction and post-processing stages, also It is to enter reactor from raw material phosphorus oxychloride and propylene oxide, until obtaining the total time for the TCPP finished products for meeting commercial standard. The continuous flow process of TCPP productions refers to that the entire technical process of the stage of reaction and post-processing stages continuously flows, that is, is connected The continuous raw material phosphorus oxychloride and propylene oxide, pilot process of being added does not have any stop and waiting, is continuously available and meets commercial standard TCPP finished products.

European patent EP 0398095B1 is disclosed phosphorus oxychloride and propylene oxide in TCPP as solvent, titanium tetrachloride To be reacted under conditions of catalyst, then after strong acid washing, separatory funnel liquid separation, washing, alkali cleaning and distillation drying etc. Reason obtains finished product.Although the method use continuous production processes to prepare TCPP, due to needing the behaviour such as liquid separation, cooling in the process Make, use traditional consersion unit (including cascade reaction cluster, stirred autoclave, glass flask etc.), so needing more Secondary stop waits for, therefore is discontinuous flow production technology.It is mentioned in the patent, the residence time at 0.5-1.6 hours, can obtain The TCPP finished products of high quality.More specifically, three stirred autoclaves for carrying heat-exchanger rig have been used in the embodiment of the patent, And the residence time of each reaction kettle is maintained at 45 minutes, described in residence time of only reaction for referring to residence time, then In addition the last handling processes such as subsequent pickling, alkali cleaning, washing and drying, production technology total time can significantly extend, it is entire raw Producing the time will be more than a few hours.So the technical solution of the patent disclosure be discontinuous flow production technology, and react it is total when Between it is long, reaction efficiency is not affected significantly.Meanwhile needing to wash using strong acid in the technique last handling process, but TCPP products Stability is very poor under strongly acidic conditions, and product can be caused to decompose in this way and generate byproduct so as to cause under product yield and quality Drop, alkali charge rise.In addition, using TCPP as solvent in reaction, common condition of no solvent is compared, production is considerably increased Cost reduces production efficiency.Chinese patent CN1034206A discloses a kind of the continuous of alpha-halogenate alkyl phosphate (such as TCPP) Manufacturing method.I.e. under the action of the compound of beryllium and phosphorus trichloride mixed catalyst, using multistage continuous reaction tank, continuously Adverse current carries out base extraction and water washing, finally carries out reduction vaporization dehydration and obtains product.This method compared with prior art, though It has so used continuous processing to produce TCPP, but has used a large amount of retort in the process, settler, the tradition reaction such as agitating shaft Device, centre necessarily have a stop and waiting process, and the time used is not short enough, generation efficiency is not high enough, still falls within aforementioned discontinuous Flow production technology.The technology is mentioned simultaneously, and TCPP total reaction times are relatively long, is reached more than a few hours.In addition, in the patent The beryllium oxide used is a kind of toxic articles, so the technical solution should not be promoted the use of.As it can be seen that technical side described in the patent Case, neither continuous flow production technology, also makes apparent technological improvement, and in reaction process in terms of no reproduction efficiency Catalyst is made using toxic articles, greatly restriction effect is played for commercial introduction application.

To sum up, the production technology of prior art preparation TCPP, is the production technology of discontinuous flow, that is, prepares TCPP's The stage of reaction and the technique of post-processing stages there is no continuously integrate with matching together with, but two mistakes independently Journey, that is, the stage of reaction and post-processing stages have stop or waiting.The prior art is difference to the improvement of TCPP production technologies For the improvement of the stage of reaction and post-processing stages, wherein typical technology is as follows：

United States Patent (USP) US7820845B2 is mentioned, the product (phosphorous acid obtained after phosphorus trihalide and alchlor successive reaction Ester), it is transferred to a reactor in batch or continuously, and react with alkylene oxide (i.e. epoxide), is finally contained with caustic dip There is the crude product of remaining alkylene oxide.The patent points out, to ensure continuous reactiveness, the flow velocity of phosphorus trihalide should be 100 liters/ Hour to 1000 ls/h, preferably 200 ls/h to 500 ls/h.This method only realizes company in stage of reaction technique It is continuous, it is not directed to post-processing stages technique, is not the Total continuity stream production technology of TCPP.Meanwhile the embodiment 1 and reality of the patent Example 2 is applied, the reaction time has reached 6 hours, and to complete post-processing stages again, production technology total time will be longer, this is obviously Production efficiency is greatly reduced, this patent uses discontinuous flow production technology.

The production technology of phosphate or phosphite ester has certain similar, and reaction step is mainly phosphorus trihalide or zirconyl oxyhalides Phosphorus and epoxide occur opening and obtain various phosphates or phosphite ester.But different phosphates or phosphorous Architectural difference existing for acid ester derivant (such as substituent group type, quantity and the position of substitution difference), can cause to synthesize various phosphorus Physicochemical properties (such as molten boiling point, the dissolving of raw material, reaction intermediate and product needed for acid esters or phosphite derivative object Degree, reactivity and stability, even reaction mechanism and selectivity etc.) it is totally different, and then cause corresponding synthetic route and There are bigger differences for production technology, it is difficult to mutually use for reference, also can not mutually transplant and indiscriminately imitate, need to be related to during specific The physicochemical properties of compound specially design and develop targetedly technical process, condition and parameter.Therefore for involved by this patent And TCPP continuous flow production technologies, the production technology of different phosphates or phosphite ester cannot use for reference directly, not have reference Value.

Also there is the trial to the continuous aftertreatment technologies of TCPP in pertinent literature.Chinese patent CN 105837621A are disclosed A kind of after-treatment device and method of phosphate flame retardant carry out phosphate crude product inverse by caustic wash tower, water scrubber successively Stream contact is then added to thin film evaporator or molecular distillation evaporator obtains finished product, and wherein alkali cleaning and washing time of contact is respectively 7~20min and 8~30min.The patent only realizes the continuous of post-processing stages, but there is no post-processing stages with react Stage combines realization serialization, therefore is not TCPP Total continuity stream production technologies.And the patent be only completed alkali cleaning and Two step countercurrent washings are washed, the operating time is at least in 15min, though the time upper existing shortening compared with autoclave is washed, production effect Rate still needs to improve.Because this method is not continuous from post-processing is reacted to, use discontinuous flow production technology, obtain at Product inevitably will appear sour regurgitation and have to be hoisted containing features, product qualities such as aldehyde type impurities.

By the analyses of above-mentioned documents as it can be seen that though the prior art realizes the continuity in a certain stage, complete There is still a need for the long periods for entire reaction.In the prior art in addition to cannot achieve the efficient Total continuity stream production technology of TCPP, also deposit Impurity is more, the easy sour regurgitation of poor storage stability, wastewater discharge is big and phosphorus content is excessively high, there are the problems such as security risk urgently It is to be solved.

It is well known that existing TCPP production technologies have PART EPOXY third in process of production since the reaction time is long Alkane is oxidized to aldehyde compound by phosphorus oxychloride, and wherein 2- methyl alkene valeral is main impurity, which has special stench, It has good intermiscibility with TCPP, water is practically insoluble in, even across post-processings such as a series of alkali cleaning, washing and dehydrations Still suffer from residual.By the detection discovery to existing finished product, 2- methyl alkene valeral residual quantities are not less than 100ppm, some finished products Residual quantity be even as high as 200-300ppm, seriously affect the quality of TCPP finished products.

Chinese patent CN100549130C discloses the method that TCPP is prepared and removed aldehyde type impurities, that is, is obtaining TCPP After crude product, the hydroxylamine hydrochloride solution of aldehyde compound equivalent is added, is allowed to generate the oxime for being dissolved in water with by-product aldehyde reaction, lead to Later continue washing process to remove oxime, and then aldehyde type impurities content in TCPP finished products is made to reduce.This method is disadvantageous in that： First, needing to increase additional water washing operations, time cost is increased, also increases waste water, it is not only uneconomical but also not environmentally；Second is that Hydroxylamine hydrochloride is immiscible with product, and reaction process is slow, and aldehyde type impurities removal may be caused not exclusively to reduce product quality；Three It is that hydroxylamine hydrochloride is of high cost, and the parts HCl therein can decompose TCPP finished products reduction yield.

In addition to hydroxylamine hydrochloride solution is added, aldehyde type impurities can also be removed by way of oxidant is added.It is Chinese special In sharp CN101775031A, with Mn, Cr, Fe, O, S, Cl, Br, the high-valence state oxide or peroxide of the elements such as I composition or its Acid and the stink that TCPP is removed by aqueous solutions such as sour sylvite, the sodium salts formed.Chinese patent CN102002068A directly uses smelly Oxygen aoxidizes the aldehyde material to give an offensive smell, to achieve the purpose that deodorization.Chinese patent CN 102775439B disclose a kind of TCPP Preparation method, in last handling process, with organic peroxide handle crude product, will slightly be produced using the oxidisability of peroxide Aldehyde material in product is oxidized to acidic materials, and oxidizing temperature is 60-80 DEG C, then using alkali cleaning, washing and decompression dehydration The product of low smell is made.The patent introduces new organic compound (organic peroxide) in processing procedure, and processing is endless Plenary session leads to the decline of TCPP final product qualities, directly affects TCPP final product qualities.If in addition, be added amount of peroxides it is on the high side, Or reaction condition control is inaccurate, there are excessive oxidations, generate the risk of new impurity.It is well known that organic peroxide is A kind of inflammable and explosive compound, especially under heating state (patent uses 60-80 DEG C), danger coefficient is multiplied, should There is certain danger during the method use that patent provides.Such methods common problem is that additional increase is needed to go The step of except acidic materials, brings many problems that additive is such as added and increases cost, increases the cost of investment of other equipment, increase The process time has been added to reduce process efficiency, additive residual can influence quality of finished etc..

The TCPP finished products of prior art production can there is a phenomenon where sour regurgitations during storage and use.If will have sour regurgitation The TCPP finished products of phenomenon are used for combined polyether formula, since the acidic materials generated in TCPP can be neutralized further in combined polyether Amines catalyst, therefore combined polyether formulation section can be caused or be damaged completely, lead to that mass and performance cannot be produced Qualified polyurethane foam, or even the process of production foam fall flat.It can be seen that the stability of TCPP finished products makes downstream With particularly significant, the stability of especially acid value is more notable, the income of downstream manufacturers will be directly affected, if being avoided that sour regurgitation Phenomenon occurs, and will greatly promote TCPP finished product use reliabilities.

Chinese patent CN103408584A mentions a kind of method that high hydrolysis resistance prepares TCPP, i.e., TCPP crude products is added In water, the TCPP of high hydrolysis resistance is made using washing and dewatering and filtering for hydrolyzed under acidic conditions processing.The water of its acid condition It is 0~10 DEG C to solve temperature, pH value 2~4, under strong stirring temperature adjustment add acid for adjusting pH≤5 to -5~50 DEG C, hydrolysis 60~ 180 minutes, diluted alkaline is used in combination to adjust pH value to 8~9, temperature is adjusted to 50~90 DEG C, be washed with deionized again after stratification, Vacuum distillation dehydration refilters to obtain high hydrolysis resistance product.The good product of thermal stability in order to obtain, the patent need separately to add Add additional acid to be compared stringent adjusting to the pH of reaction solution to handle, process is troublesome in poeration, the temperature control of acid cleaning process It is required that high, the residence time is long, influences product yield.Even if the patent system obtained the TCPP products of the lower high hydrolysis resistance of acid value, But still sour regurgitation phenomenon can not be avoided.Although Chinese patent CN106699804A discloses a kind of TCPP that heat storage stability is good productions Method is warming up to 65 DEG C with the speed of 10 DEG C/min, is added dropwise that is, by phosphorus oxychloride and catalyst (while including alcohol radical and metal) Auxiliary agent after keeping the temperature 30 minutes, is cooled to 40-45 DEG C of dropwise addition propylene oxide, heat preservation aging 4 hours, wherein the auxiliary agent is chlorination Normal-butyl pyridine.Although reaction solution that this method the obtains heat storage time is long, due to not by more handling, gained at Product still contain the substances such as catalyst and auxiliary agent, the impurity that can influence that downstream uses.Chinese patent CN103833784B is disclosed Using the catalyst containing metal and alkane root, 60~80 DEG C of progress agings are warming up to after raw material is added dropwise, Ageing solution acid is measured after 3 hours Value be≤0.2mgKOH/g when discharge.Likewise, although the finished product heat storage of gained is stablized, without remove corresponding catalyst and The impurity of generation influences the follow-up use of TCPP.As it can be seen that the prior art can increase substantially in terms of improving TCPP finished product stabilities Add special processing step, but these technical solutions can reduce the quality in some aspects of TCPP finished products, increase TCPP finished products Production time and cost of material.In addition, the sour regurgitation that can not solve the problems, such as TCPP finished products of the prior art.

The method that prior art last handling process improves TCPP final product qualities, only improves some performance, such as reduce Acid value, the content etc. for reducing aldehyde type impurities, but can not realize that the comprehensive of multiple performances is improved simultaneously, and can not be made not sour regurgitation and Finished product without aldehyde type impurities.Post-processing approach used in the prior art is to increase step or add new substance, is caused into This increase, time-consuming, efficiency is low, and the novel substance of addition will necessarily influence TCPP final product qualities.What is more important, the prior art There is no any solution for the sour regurgitation of TCPP.In addition, prior art last handling process and reaction process are not incorporated into Together, it is two processes independently, the technique and equipment of use are different, cause production efficiency not high and increase into This.

In addition, existing production technology, there is also the last handling process time is long, water consumption is big, and washes phosphorus content compared with It is high, it is difficult to the problem of harmless treatment.There are many organic and inorganic impurities due to containing in waste water obtained by prior art, cannot be direct It applies mechanically, generally requires and handled by hazard-free and biochemical, can just be discharged after reaching standard, increase wastewater treatment processing cost.Together When due to wherein phosphorus content it is higher, existing production firm generally requires and is first diluted, then when handling phosphorous washes Biochemical treatment is carried out again, virtually increases wastewater flow rate again, and then increase processing cost.Since wastewater flow rate is big, wastewater treatment Recycling occupies no small ratio in the entire production costs of TCPP, and usually, industrial water and cost for wastewater treatment can account for whole The 20-30% of a TCPP production costs, water consumption and treating capacity cross conference to directly result in production cost excessively high, reduce profit.

Further, since the stage of reaction and post-processing stages of the prior art are two processes independently, without continuous Ground integrate with matching together with, cause the prior art can not be by the difference between the crude product of different batches made from the stage of reaction Control causes finishing time and lye amount that can not be carried out according to the actual conditions of each batch crude product in minimum range Accurate adjustment can only ensure that the crude product warp of poor batch is located later with enough finishing times and enough lye amounts Become qualified commercial product after reason, the risk for substandard product occur is reduced with this；But relative to the thick of preferable batch Product will result in the waste of the waste and lye amount of finishing time, increase production cost and environmental pollution.

To sum up, although including being made some attempts in continuous synthesis and continuous post-processing in TCPP continuous production processes, phase There is improvement than caldron process, but still there are following main problems：

1. failing to realize the production technology that is simple and efficient from raw material to qualified commercially available finished product, production process is complicated, it is more to need Secondary stop waits for；

2. the stage of reaction and post-processing stages do not combine continuously, but two processes independently, It does not use a set of equipment to be directly realized by production and the last handling process of TCPP, causes production efficiency not high yet；

3. technique total time is long, production efficiency is low；

4. needing to increase the aldehyde type impurities in additional step processing finished product, it is readily incorporated while causing production cost to rise New impurity influences final product quality and follow-up use；

5. finished product has different degrees of sour regurgitation phenomenon, downstream use is influenced；

6. generating the high waste water of a large amount of phosphorus contents in last handling process, processing is high, it is difficult to recycle.

In the prior art, acid value stabilization (not sour regurgitation) can not also be made, the content of aldehyde material (is free of aldehydes for 0 Matter) and without the TCPP finished products of the corresponding metal cation of catalyst (content of the metal cation is 0), also do not open It is simple, efficient, environmentally friendly to send out production process, and can guarantee the technique of finished product high-quality, i.e.,：Reaction process and last handling process connect Together with continuing integration and matching, the TCPP finished products for meeting commercial standard are simply and efficiently obtained from raw material, moreover it is possible to take into account finished product High-quality (being free of aldehyde type impurities, not sour regurgitation), environmental friendly property (reducing the phosphorus content and waste water total amount in waste water) and low cost (increasing removal step without additional).

Invention content

In view of the deficiencies of the prior art, technical problem to be solved by the invention is to provide a kind of lifes of the Total continuity stream of TCPP Production. art, that is, by the stage of reaction and post-processing stages, technique carries out continuously, incessantly as a whole, raw material (POCl₃, PO, catalyst) continuously enter reactor feed mouth, continuously obtain meeting city in reactor outlet The TCPP finished products for selling standard realize and quickly prepare high quality tricresyl phosphate (the chloro- 2- propyl of 1-) ester (TCPP) finished product.Institute of the present invention The TCPP Total continuity stream production technologies stated not only realize efficiently production, high quality product and stable storing, and TCPP finished products are free of aldehyde Class impurity, not sour regurgitation, and the wastewater flow rate that technique generates is few, phosphorus content is low, is good for the environment, and it is suitble to security industry metaplasia Production.

Continuous production processes refer to being mutually linked between each production stage of production system in production process, ensure to hold on the whole Reforwarding row, but allow to stop in each step and wait for.The one kind of Total continuity stream production technology as continuous processing is a kind of quick Efficient whole process continuous processing, has the characteristics that the used time is short, efficient, easy to operate, is uninterruptedly added in the process former Material, uninterruptedly produces finished product, material (includes the reaction of raw material, intermediate, product, solvent etc. in the process Mixture) continuously flow, it is not interrupted, does not stop waiting, production and last handling process are continuous, carry out incessantly, The finished product for meeting commercial standard is continuously produced, and is a kind of chemical process of " assembly line " formula.Work as work Skill operation is when reaching stationary state, and the state parameters such as composition, temperature of material not time to time change on any position in reactor is Steady-state process, thus production process and final product quality are all stable.

The present invention adopts the following technical scheme that：

It is an object of the present invention to provide a kind of tricresyl phosphate (the chloro- 2- propyl of 1-) ester finished product (TCPP finished products), acid values Stablize and the content of aldehyde type impurities is 0, acid value (mg KOH/g)≤0.1, moisture content (wt.%)≤0.1, color and luster (APHA)≤50, (25 DEG C, mPas) of viscosity is 50-80.TCPP finished products namely of the present invention not sour regurgitation, be free of aldehyde type impurities.

Further, TCPP finished products provided by the invention do not contain 2- methyl alkene valerals.

The content that the present invention measures aldehyde type impurities using GC-External Standard method is said for detecting 2- methyl alkene valerals Bright specific detection method：

Draw standard curve：The accurate 2- methyl alkene valeral standard items for weighing certain mass, solvent is made using anhydrous propanone, It is several (being not less than 3 samples) that it is configured to standard solution of the content between 0.02ppm-0.2ppm respectively.Pass through gas-chromatography Analysis obtains the corresponding data of different content and peak area under certain condition, draws standard curve：

Y=kX+b.

In above formula, the content of aldehyde, ppm in Y-sample introduction；

K-slope of standard curve；

X-peak area；

B-standard curve intercept.

Sample measures：Accurate weighing 0.1000g TCPP samples are added in 10ml anhydrous propanones, concussion to being completely dissolved, Sample introduction is analyzed.It brings peak area data into calibration curve formula and obtains the aldehyde of sample introduction TCPP.Practical aldehyde in TCPP For 100Y (ppm).

The not sour regurgitation refers to that TCPP finished product acid values do not change, particularly, the acid value (acid of TCPP finished products Value) acid value is constant during storage, transport or downstream user use.Acid value measuring uses ASTM D974-2012 In method, concrete operations are as follows：

The sample of about 10-15g is weighed, it is accurately weighed, it is placed in 250ml conical flasks.30ml absolute ethyl alcohols are added, until sample It is completely dissolved, 0.5ml phenolphthalein indicators is added, shake to colourless homogeneous transparent.It is instilled to presentation blush with KOH standard solution, And kept for half a minute colour-fast, as titration end-point.

Same method is not added with sample and does blank test.

Acid value calculates as follows：

X=(V₁-V₂)·C/m

In above formula, the acid value of X-sample, mg KOH/g；

V₁The dosage of KOH standard solution, ml when-sample titrates；

V₂The dosage of KOH standard solution, ml when-blank titration；

The concentration of C-KOH standard solution, g/L；

The quality of m-sample, g.

Further, it is described in order to it is simple and quick detect finished product whether sour regurgitation and sour regurgitation degree, can be by making It is characterized and is embodied with the method for burn-in test, the specific method is as follows：Take 60gTCPP samples to the aging bottle of 60ml volumes In, it is put into after being sealed in the baking oven of 100 DEG C of constant temperature and keeps the temperature 3h, front and back comparison acid value variation.If acid value does not change, Illustrate not sour regurgitation.

Further, the TCPP finished products acid value≤0.07mgKOH/g, preferred acid number≤0.05mgKOH/g, more preferably acid Value≤0.01mgKOH/g；Moisture (wt, %)≤0.07%, preferably moisture (wt, %)≤0.05%；Viscosity (25 DEG C, mPas) For 65-72mPa.s, preferably 68-70mPa.s；Color and luster (APHA)≤30, preferably color and luster (APHA)≤20.

Further, the TCPP finished products are free of the corresponding metal cation of catalyst, obtained TCPP quality of finished Higher.Preferably, the catalyst is TiCl₄, corresponding metal cation is Ti⁴⁺；Preferably, the catalyst is AlCl₃, corresponding metal cation is Al³⁺；Preferably, the catalyst is ZnCl₂, corresponding metal cation is Zn^{2 +}；Preferably, the catalyst is MgCl₂, corresponding metal cation is Mg²⁺；Preferably, the catalyst is FeCl₃, Corresponding metal cation is Fe³⁺。

The residual of the corresponding metal cation of catalyst is detected using ICP-OES 7000DV instruments, and specific method is such as Under：

Drawing curve：The standard substance for accurately weighing metallic element to be measured uses certain density HNO₃Match respectively It is several that standard solution of the content between 1ppm-100ppm is made；The blank solution for separately preparing same acidity is a.Pass through instrument Analysis obtains the spectral absorption intensity data of the metallic element standard solution of various concentration, draws working curve：

I=AC

In above formula, I-metallic element spectral absorption intensity；

A-related coefficient；

C-metallic element concentration.

Sample treatment and measurement：The TCPP samples of accurate weighing certain mass, using Muffle furnace ashing processing to it is organic at Divide and decomposes completely；Use certain density HNO₃Solution is shifted to ash content dissolution process, after depickling and is determined using 100ml volumetric flasks Hold.It tests and analyzes to obtain the spectral absorption intensity I of element by instrument, substitutes into working curve and obtain the dense metal of sample after constant volume Concentration of element C, and then calculate metal cation content therein according to TCPP sample qualities are weighed.

Second object of the present invention is to provide a kind of Total continuity stream production work of tricresyl phosphate (the chloro- 2- propyl of 1-) ester finished product Skill, the production technology carry out in integrated continuous flow reactor, and the production technology includes the stage of reaction and rear place Reason stage, the stage of reaction and post-processing stages carry out continuously, incessantly, in the integrated continuous flow reactor Feed inlet propylene oxide, phosphorus oxychloride, catalyst, lye, water is uninterruptedly added, go out in the integrated continuous flow reactor Material mouth uninterruptedly obtains tricresyl phosphate (the chloro- 2- propyl of 1-) ester (TCPP) finished product, TCPP production technologies total time≤10 minute.

Further, described its acid value of TCPP finished products is stable and the content of aldehyde type impurities is 0, and acid value (mg KOH/g)≤ 0.1, moisture content (wt.%)≤0.1, color and luster (APHA)≤50, (25 DEG C, mPas) of viscosity is 50-80.

Further, the TCPP finished products that prepared by the present invention do not contain 2- methyl alkene valerals.

Further, TCPP finished products acid value≤0.07mgKOH/g that prepared by the present invention, preferred acid number≤0.05mgKOH/g, More preferable acid value≤0.01mgKOH/g；Moisture (wt, %)≤0.07%, preferably moisture (wt, %)≤0.05%；Viscosity (25 DEG C, mPas) it is 65-72mPa.s, preferably 68-70mPa.s；Color and luster (APHA)≤30, preferably color and luster (APHA)≤20.

Further, the TCPP finished products that prepared by the present invention be free of the corresponding metal cation of catalyst, obtained TCPP at Product quality higher.Preferably, the catalyst is TiCl₄, corresponding metal cation is Ti⁴⁺；Preferably, described to urge Agent is AlCl₃, corresponding metal cation is Al³⁺；Preferably, the catalyst is ZnCl₂, corresponding metal sun from Son is Zn²⁺；Preferably, the catalyst is MgCl₂, corresponding metal cation is Mg²⁺；Preferably, the catalyst is FeCl₃, corresponding metal cation is Fe³⁺。

The present invention creatively by the stage of reaction and post-processing stages as a whole technique continuously, incessantly into Row, raw material continuously enter reactor feed mouth, continuously obtain meeting commercial standard in reactor outlet TCPP finished products are truly realized the Total continuity stream production of TCPP, realize and quickly prepare high quality tricresyl phosphate (the chloro- 2- propyl of 1-) Ester (TCPP) finished product.Surprisingly, using the technique of the present invention, be made the prior art can not acid value obtained it is stable and The content of aldehyde type impurities is 0, the TCPP finished products that the content of the corresponding metal cation of catalyst is 0, other indexs also superior to The product of the prior art, and the wastewater flow rate that technique generates is few, phosphorus content is low, is good for the environment, and it is suitble to security industry Production.The production technology of the present invention is completed in an integrated continuous flow reactor, and floor space is small, has greatly saved factory Room land used and cost.

Further, the post-processing stages include after successive reaction continuous vacuum removing residual epoxide propane (PO) and Low boiling impurity, continuous washing and continuous liquid separation, continuous drying dehydrating operations.

Further, the TCPP production technologies total time be 0.5~10 minute, more preferable 2~8 minutes, most preferably 4~ 6 minutes.The TCPP production technology total times, include the total time of the stage of reaction and post-processing stages, that is, from raw material Phosphorus oxychloride and propylene oxide enter reactor, until obtaining the total time of standard compliant TCPP finished products.

Further, the time (T1) of the stage of reaction is 0.2~5 minute, the post-processing stages time preferably 0.3~5 Minute.Specifically, continuously the time (T2) of vacuum removal residual epoxide propane (PO) and low boiling impurity is preferably 0.1~1 Minute, the time (T3) of continuous washing and continuous liquid separation is preferably 0.1~2 minute, and the time (T4) of continuous drying dehydration is preferred It is 0.1~2 minute.

Raw material propylene oxide, phosphorus oxychloride, catalyst are completed to react by the present invention through integrated continuous flow reactor successively With two operation stages of post-processing, the TCPP finished products of good quality are obtained.TCPP Total continuities stream production technology of the present invention, Moment any time in process of production, propylene oxide and phosphorus oxychloride are all enough, and there is no need to add dropwise addition Operation bidirectional, and each material is all enough in last handling process, belongs to completely new production technology.The prior art cannot accomplish Raw material is disposably enough to be filled up, and is required to be added portionwise or be added dropwise mode to realize.

Further, the catalyst is lewis acid catalyst or corresponding Lewis acidic ionic liquid catalyst.

Further, the catalyst be selected from alchlor, titanium tetrachloride, positive four butyl ester of metatitanic acid, zinc chloride, magnesium chloride, It is one or more in iron chloride and corresponding ionic-liquid catalyst.

Further, the catalyst amount is POCl₃The 0.01%~1% of weight, preferable amount be 0.01%~ 0.5%, more preferably 0.1%~0.5%, more preferably 0.2%~0.4%.Specific dosage is according to different catalysts kind Class and the physical condition of reaction (needing the conditions such as comprehensive matching different flow, different temperatures) and determine.Further, epoxy The dosage of propane is POCl₃3.0~5.0 times of molal weight, preferably 3.0~4.0 times, more preferably 3.0~3.5 Times, more preferably 3.01~3.1 times.

Further, the temperature of the stage of reaction is 0~200 DEG C, it is preferable that 0~30 DEG C, more preferable 30~150 DEG C, more It is preferred that 50~120 DEG C, more preferable 60~80 DEG C；It is further preferred that 100~200 DEG C；It is further preferred that 150~200 DEG C.

Further, the temperature of the post-processing stages be 30~200 DEG C, preferably 30~50 DEG C, more preferable 50~180 DEG C, more preferable 60~150 DEG C, more preferable 150~200 DEG C, it is further preferred that 100~200 DEG C.

Usually, the reaction temperature of industrialized production TCPP is 40~90 DEG C at present, and main cause is current producer Formula needs could cause under certain reaction temperature, but temperature is excessively high and ground causes runaway reaction, easily generate impurity and have Security risk.Using Total continuity stream production technology of the present invention, raw material can be made to cause and react at lower temperatures, reaction is enable to exist Cause at 0~40 DEG C；Reaction can also be better controlled reaction under the higher reaction temperature of the prior art, makes reaction Can at 90~200 DEG C balance movement, avoid the generation of side reaction and the appearance of safety problem.It is industrialized at present to post-process Journey, especially washing process temperature general control more cause wash time long at 75~95 DEG C, and detersive efficiency reduces same When, washing effect can also decline, and keep acid value higher.When temperature higher, washings are met boiling, can greatly reduce washing effect Fruit, while decomposition of the TCPP products in washing process can be caused, reduce product quality and yield.Use the Total continuity of the present invention Production technology is flowed, can be washed and be obtained low acid value and the finished product of qualification at lower temperatures, enable washing at 30~50 DEG C The lower post-processing operation for completing washing.At the same time, using the Total continuity stream production technology of the present invention, wash time is contracted significantly It is short, enable washing implement under higher temperature (150~200 DEG C) and will not cause TCPP products in washing process point Solution and loss.

Further, propylene oxide (PO) can be with one charging or multiply charging.

Further, the phosphorus oxychloride (POCl containing catalyst₃) can also one charging or multiply charging.

Further, after the completion of the stage of reaction, reaction solution is continuously sloughed to remnants PO in reaction solution under vacuum conditions While, the low boiling impurity that reaction process generates can be removed together.This has positive effect for the quality for improving finished product.

Further, it sloughs before the TCPP crude products after PO add alkali, first plus water carries out being sufficiently mixed progress with crude product Washing, is acid cleaning process, carries out alkali cleaning later, finally washed.

Further, the water that acid cleaning process is added is POCl₃The 5%~100% of feedstock quality, preferably 10%~ 80%, more preferable 20%~50%.

Further, the alkali used when alkali cleaning is selected from water soluble metal hydroxide, water soluble quaternary ammonium hydroxide, water-soluble Property tertiary amine, preferred alkali metal hydroxide or alkaline earth metal hydroxide, more preferable sodium hydroxide, potassium hydroxide, sodium carbonate, carbon Sour hydrogen sodium, potassium carbonate, saleratus or lithium hydroxide.

Further, the lye mass concentration be 0.1%~40%, preferably 0.5%~20%, more preferable 1%~ 8%.

Further, the lye dosage is POCl₃The 2%~100% of feedstock quality, preferably 5%~50%, more preferably 10~30%.

Further, the water consumption washed after alkali cleaning is POCl₃The 10%~100% of feedstock quality, preferably 20%~ 80%, more preferable 40%~60%.

The prior art is most of to be washed using first addition acid in order to remove acid instability impurity in TCPP crude products It washs, then carries out the subsequent operations such as alkali cleaning, washing.It is complicated for operation, time-consuming, and TCPP product itselfs time mistake in acid condition It is long, it will hydrolyze, yield is caused to decline.For the last handling process of TCPP crude products, pickling and alkali cleaning are the prior art Two independences, separated process, need two covering devices to realize.Acid cleaning process needs additional addition acidic materials (strong acid, concentration High acid, hydrochloric acid, sulfuric acid, phosphate aqueous solution), and TCPP crude products and the time of contact of acid are long, pickling time half an hour arrives A few hours, alkali cleaning again, is washed again after alkali cleaning after pickling, make TCPP products pH value be neutrality, alkali cleaning, washing time also distinguish Need half an hour to a few hours.Its disadvantage：Pickling can lead to the hydrolysis of TCPP, and yield is made to reduce；Additional acid is added in pickling, increases The burden for having added alkali cleaning, increases production cost, also increases time and the environmental pollution of post-processing.

Acidic materials are added without additional in the acid cleaning process of the present invention, but seamless by the stage of reaction and post-processing stages Docking, being previously added washing by the water for needing alkali cleaning realizes the effect of acid cleaning process, and TCPP is thick made from the stage of reaction Product and the mixed solution of water are faintly acid, using TCPP Total continuity stream production technologies, are completed under weak acid environment The operation of pickling impurity removal matter, and the time of pickling has been greatly shortened, it is preferably 1~10 second acid cleaning process duration, more excellent It selects 2~6 seconds.It should be noted that different from the pickling time of prior art half an hour to a few hours, acid cleaning process of the invention Time control the second grade in the range of, the time is considerably shorter than the prior art.Therefore the acid for passing through the present invention is prepared according to the washing of process Obtained TCPP final product quality highers, stability is more preferable, and without additional acidic materials are added, and not only ensures yield, reduces Production cost, and shorten the production time, improve final product quality.The Total continuity stream production technology that the present invention uses, by pickling, alkali Wash, wash the integration of three processing efficients and be carried out continuously, and can be completed (in 10 seconds) in a short period of time pickling, alkali cleaning, Water washing operations have obtained TCPP finished products that are more pure and stablizing in the case where ensureing that product does not decompose with high yield.And Under conditions of continuous flow production technology of the present invention, the water that alkali cleaning needs are firstly added into TCPP crude products generates weak acid ring Border, then it is proportionally added into the TCPP finished products obtained after caustic dip not sour regurgitation, it avoids adding after directly adding alkali cleaning or first acid adding Alkali obtains the finished product of sour regurgitation.

Further, prior art alkali cleaning and washing after waste water phosphorus content all in 2000ppm or more, due to existing way There is production material fluctuation, the waste water phosphorus content of the low production batch of some yields to be even as high as 7000~8000ppm or more, and And direct recovery cannot be carried out, and needed before discharge by micro- containing the impurity generated in building-up process in waste water The modes such as biology are handled, and the phosphorus content in waste water is reduced to 8ppm or less.Work is produced using the Total continuity stream of the present invention Skill, because the extent of reaction is high, while side reaction and impurity are few, needed in crude product obtained by the reaction the phosphorous raw material being removed, Phosphorous intermediate and other byproducts are less, and water phase phosphorus content significantly reduces after making washing.By detection, Total continuity stream produces work The phosphorus content of alkali-wash waste water and washing waste water that skill obtains is in 100~1000ppm.Accordingly, due to continuous flow production technology pair The control of reaction impurities is more preferable, and the impurity that water phase contains after washing is also less, post-processes the waste water of production and can be applied mechanically, greatly The earth reduces the dosage of water and the generation of waste water.By calculating, in the case where not applying mechanically, Total continuity stream of the present invention produces work The alkaline cleaning procedure water consumption of skill saves 25%~30% than current workshop dosage, and present invention process water-washing process is than current vehicle Between save 55%~60%, whole water consumption declines 40~45%.Water phase after water phase either after alkali cleaning, or washing, It can be applied mechanically after use, realization further controls cost.

Reaction process can carry out in the absence of a solvent, it is also contemplated that adding solvent.Selected solvent have benzene, Toluene, dimethylbenzene, hexamethylene, hexahydrotoluene, carbon tetrachloride, chloroform, dichloromethane, dimethyl carbonate, ethyl acetate, Acetone, acetonitrile etc., these solvents can terminate the later removing propylene oxide stage in reaction, be removed together with propylene oxide. It is special, it is also an option that TCPP is as solvent, using TCPP as the benefit of solvent be after reaction terminates, need not be from body System removes, because own is exactly product.Toward the mode of reaction system solubilizer, solvent can be selected to be separately fed to reactant In system, further, the flow velocity of the solvent is 0.1~2.5L/h, preferably 0.3~2.0L/h, more preferable 0.5~1.6L/h； Solvent can also be selected first to be mixed according to a certain percentage with a certain raw material, enter back into reaction system, flow velocity should be at this time The adduction flow of raw material and solvent.

Further, the reaction raw materials contain the phosphorus oxychloride (POCl of catalyst₃) solution flow velocity be 0.1~2L/ H, preferably 0.3~1.8L/h, more preferable 0.5~1.5L/h.

Further, reaction raw materials propylene oxide (PO) flow velocity be 0.2~6.0L/h, preferably 0.6~4.5L/h, more It is preferred that 1.1~3.4L/h.

Further, in the acid cleaning process water flow velocity be 0.008L/h~3.29L/h, preferably 0.016L/h~ 1.645L/h, more preferable 0.032L/h~1.645L/h.

Further, when the alkali cleaning water flow velocity be 0.1~3L/h, preferably 0.2~2.0L/h, more preferable 0.3~ 1.5L/h。

Further, the flow velocity of lye is 0.01L~6.0/h, preferably 0.1~3.0L/h, more preferable 0.2 when the alkali cleaning ~1.0L/h.

Further, described after alkali cleaning to wash used water flow velocity for 0.1~2.5L/h, 0.2~1.8L/h, more preferably 0.4~1.5L/h.

It should be noted that the reaction bottom in actual production used in (including in laboratory, pilot scale, actual production process) Object, catalyst etc. have the deviation of ± 2 percentage points of mass concentration；Warm area temperature has ± 3 DEG C of deviation；Production time meeting There is the deviation of ± 5s.

Further, the integrated continuous flow reactor includes reaction member and post-processing unit, raw material epoxy third The reacted unit of alkane, phosphorus oxychloride, catalyst completes the stage of reaction, then post-treated unit obtains the TCPP for meeting commercial standard Finished product.

Further, the post-processing unit is for realizing the continuously vacuum removal residue ring of the reaction solution after reacting Ethylene Oxide (PO) and low boiling impurity, continuous washing and continuous liquid separation, continuous drying dehydrating operations.

Further, continuously vacuum removal residual epoxide propane (PO) and low boiling impurity can pass through continuous rectifying tower To complete.Further, preferably 50~200 DEG C of the temperature of rectifying, more preferable 80~150 DEG C, more preferable 90~120 DEG C.

Further, the reaction member and post-processing unit separately include one or more functions unit, functional unit It is combined by warm area and reactor module or reactor module group Optimized Matching, utilizes different warm areas and reactor module or reactor Synergistic effect between the Optimized Matching of module group and each section of consersion unit makes the production technology total time of finished product foreshorten to 10 It in minute, or even foreshortens within several minutes, greatly improves the efficiency of production technology.Due to using continuous flow production technology, Production time is short, and production technology total time, multiple operating process of entire technique can be in very high temperature within 10 minutes Degree is lower to carry out, and will not cause the decomposition and loss of finished product.

Further, the reaction member of the continuous flow production technology includes at least one warm area, it is preferred that described Reaction member includes 3 warm areas：Warm area 1, warm area 2 and warm area 3；Reaction raw materials POCl₃Enter warm area 1, temperature through constant flow pump with PO Area 2 and warm area 3 complete mixing, reaction causes and complete the processes such as reaction.By to each warm area reactor module or reactor Module group carries out collocation and the control to temperature, and the reaction heat that the heat that reaction is generated removes or supply needs makes open loop add At reaction can in reaction member it is steady, controllable and safely and efficiently complete.

Further, 3 warm areas of reaction member can exist simultaneously, and functional unit is made to achieve the effect that different (reactions Mixing, initiation, reaction etc.), can also be used alone, only retain a warm area, can also be continuously completed the whole of the stage of reaction A process, then can be obtained the TCPP finished products for meeting quality by post-processing stages.

Further, 0~200 DEG C of the selection process temperature of warm area 1, more preferable 30~150 DEG C, more preferable 40~100 DEG C.

Further, the selection process temperature of warm area 2 be 30~150 DEG C, more preferable 50~120 DEG C, more preferable 60~80 ℃。

Further, 30~200 DEG C of the selection process temperature of warm area 3, more preferable 60~150 DEG C, more preferable 80~120 ℃。

Further, pickling, alkali cleaning, water washing operations are completed in the warm area of post-processing unit, can be matched using 3 warm areas It closes and completes, the post-processing operation that one or two warm area individually completes pickling, alkali cleaning, washing can also be only used.For example, will The crude product obtained after vacuum processing flows into warm area 4 with water using constant flow pump, and crude product is formed with water after warm area 4 comes into full contact with Weakly acidic solution is matched can remove acid instability impurity and metal cation after temperature appropriate, at the same time, properly The lye of concentration and dosage enters warm area 5 under constant current pumping action, so that the solution obtained in warm area 4 is become alkalinity, to complete alkali Operation is washed, the solution after alkali cleaning completes water-oil separating through oil water separator, and oil phase enters warm area 6, water phase discharge or recovery, Oil water separator is the continuous oily water separating equipment known to those skilled in the art.Similarly, when oil phase enters warm area 6, water Wash water enters warm area 6 under constant current pumping action and come into full contact with completing water washing operations with oil phase.Equally, pickling, alkali cleaning It can be integrated into an independent warm area with water washing operations to be completed.

Further, integrated continuous flow reactor post-processing unit includes at least one warm area, it is preferred that after described Processing unit includes 3 warm areas：Warm area 4, warm area 5 and warm area 6.

Further, 30~200 DEG C of 4 selection process temperature of warm area, more preferable 50~180 DEG C, more preferable 60~150 DEG C.

Further, 30~200 DEG C of 5 selection process temperature of warm area, more preferable 50~180 DEG C, more preferable 60~150 DEG C.

Further, 30~200 DEG C of 6 selection process temperature of warm area, more preferable 50~180 DEG C, more preferable 60~150 DEG C.

Further, the product that warm area 6 obtains after handling completes water-oil separating through oil water separator, and reactor is discharged in water phase Or apply mechanically, oil phase enters thin film evaporator or operation is dried in molecular distillation evaporator, obtains final finished.

Further, 30~200 DEG C of the selection process temperature of thin film evaporation, more preferable 50~180 DEG C, more preferable 60~ 150℃。

Further, the Total continuity stream production technology is continuous in the integration comprising one or more functions unit It is carried out in flow reactor.

Further, it includes at least one function that the integrated continuous flow reactor, which uses having unit structure, reactor, Unit, each functional unit include at least one warm area, and each functional unit includes independently one or more reaction Device module or reactor module group are wherein serially connected between each warm area of functional unit, one in each functional unit or more A reactor reaction device module or reactor module group are connected in series or in parallel.It is possible to further use one or more work( Energy unit completes continuous flow process, can be connected in series or in parallel between functional unit.Functional unit can by one or Multiple warm area compositions, each warm area can match one or more reactor modules or reactor module group.

Further, can include buffer (Buffer vessel) between the functional unit.

Further, the quantity of the integrated continuous flow reactor feed mouth is one or more, and the integration is continuous The quantity of flow reactor discharge port is one or more.

Further, the reactor module, which is optionally any one, can realize the reaction of integrated continuous flow technique Device, the reactor are selected from microreactor (Microreactor), series connection coil reactor (Tandem loop Reactor), tubular reactor (Tubular reactor) any one or it is arbitrary a variety of.

Further, the reactor can be one or more.

Further, the material in the reactor module channel is monocrystalline silicon, special glass, ceramics, is coated with corrosion resistant coating Stainless steel or metal alloy, polytetrafluoroethylene (PTFE).

Further, the reactor is made of different functional units, and functional unit is matched with different warm areas and temperature The different temperatures in area, while being matched with the reactor module or reactor module group of different number.

Further, between the reactor module, between reactor module group, reactor module and reactor module It is respectively serial or parallel connection between group.

Third object of the present invention is to provide a kind of integrated continuous flow reactors.The Total continuity stream produces work Skill is carried out in the integrated continuous flow reactor comprising one or more functions unit.

Further, it includes at least one function that the integrated continuous flow reactor, which uses having unit structure, reactor, Unit, each functional unit include at least one warm area, and each functional unit includes independently one or more reaction Device module or reactor module group are wherein serially connected between each warm area of functional unit, one in each functional unit or more A reactor reaction device module or reactor module group are connected in series or in parallel.

Further, the reactor can be the structure of blocking, need the organizational form, the quantity that design module, The warm area that each functional unit includes, it is also necessary to develop targetedly process conditions and parameter, include division and the temperature of each warm area Setting.Functional unit includes warm area and reactor module or reactor module group, so that any of the above factor is acted synergistically, makes This continuous flow process is obtained to be achieved.Each warm area temperature and material flow can also further be combined, be allowed to use into Journey matches, and obtains better using effect.

It is possible to further use one or more functions unit to complete continuous flow process, can be gone here and there between functional unit Connection or parallel way connection.Functional unit can be made of one or more warm areas, and each warm area can match one or more reactions Device module or reactor module group.

Further, can include buffer (Buffer vessel), the buffer between the functional unit For the container with a constant volume, it is mainly used for pressure oscillation and the balance flow difference of buffer system, keeps system work more flat Surely.

Further, the quantity of the integrated continuous flow reactor feed mouth is one or more, and the integration is continuous The quantity of flow reactor discharge port is one or more.

Further, the reactor module, which is optionally any one, can realize the reaction of integrated continuous flow technique Device, the reactor are selected from microreactor (Microreactor), series connection coil reactor (Tandem loop Reactor), tubular reactor (Tubular reactor) any one or it is arbitrary a variety of.The microreactor, also known as Micro-structured reactor or micro passage reaction are that a kind of chemical reaction wherein is happened at universal lateral dimensions in 1mm and following Finite region in equipment, this kind of most typical form of finite region is miniature sizes channel.Series connection coil reactor, i.e., Be together in series coil reactor with pipeline the reactor of composition, and wherein coil reactor is that tubular reactor is made coil pipe Form.Tubular reactor be occur the middle of last century it is a kind of in a tubular form, the prodigious continuous manipulation reactor of draw ratio.It is this Reactor can be very long；It can also multitube parallel with single tube；Can also be filling pipe with blank pipe.

Further, the reactor can be one or more.

Further, the material in the reactor module channel is monocrystalline silicon, special glass, ceramics, is coated with corrosion resistant coating Stainless steel or metal alloy, polytetrafluoroethylene (PTFE).

Further, between the reactor module, between reactor module group, reactor module and reactor module It is respectively serial or parallel connection between group.

Further, the reactor is made of different functional units, and functional unit is matched with different warm areas and temperature The different temperatures in area, while being matched with the reactor module or reactor module group of different number.

Further, each warm area is matched with the reactor module or reactor module group of identical or different quantity, right Different reactor modules or reactor module group match different temperature.Different temperature is matched by the warm area to functional unit The reactor module or reactor module group of degree, matching different number and type, enable functional unit to be formed multiple and different Condition makes functional unit have the function of diversification, this so that functional unit is more flexible in use, can realize more More technological operations, such as reaction and post-processing.Further, between functional unit can series winding or and even by way of it is real Existing continuous flow production.

Further, the integrated continuous flow reactor includes reaction member and post-processing unit, raw material epoxy third The reacted unit of alkane, phosphorus oxychloride, catalyst completes the stage of reaction, then post-treated unit obtains TCPP finished products.

Further, the post-processing unit is for realizing the continuously vacuum removal residue ring of the reaction solution after reacting Ethylene Oxide (PO) and low boiling impurity, continuous washing and continuous liquid separation, continuous drying dehydrating operations.

Further, the equipment of vacuum removal residual epoxide propane (PO) and low boiling impurity is continuous rectifying tower.Into one Step ground, preferably 50~200 DEG C, more preferable 80~150 DEG C, more preferable 90~120 DEG C of the temperature of rectifying.

Further, the reaction member and post-processing unit separately include one or more functions unit, functional unit It is combined by warm area and reactor module or reactor module group Optimized Matching, utilizes different warm areas and reactor module or reactor Synergistic effect between the Optimized Matching of module group and each section of consersion unit makes the production technology total time of finished product foreshorten to 10 It in minute, or even foreshortens within several minutes, greatly improves the efficiency of production technology.Due to using continuous flow production technology, Production time is short, and production technology total time, multiple operating process of entire technique can be in very high temperature within 10 minutes Degree is lower to carry out, and will not cause the decomposition and loss of finished product.

Further, 3 warm areas of reaction member can exist simultaneously, and functional unit is made to achieve the effect that different (reactions Mixing, initiation, reaction etc.), can also be used alone, only retain a warm area, can also be continuously completed the whole of the stage of reaction A process, then can be obtained the TCPP finished products for meeting quality by post-processing stages.

Further, the reaction member of the integrated continuous flow reactor includes at least one warm area, it is preferred that institute The reaction member stated includes 3 warm areas：Warm area 1, warm area 2 and warm area 3；Reaction raw materials POCl₃Enter warm area through constant flow pump with PO 1, warm area 2 and warm area 3 complete mixing, reaction causes and complete the processes such as reaction.By to each warm area reactor module or instead Device module group is answered to carry out collocation and the control to temperature, the reaction heat that the heat that reaction is generated removes or supply needs makes out Cycloaddition reaction can be steady in reaction member, controllable and be safely and efficiently completed.

Further, 0~200 DEG C of the selection process temperature of warm area 1, more preferable 30~150 DEG C, more preferable 40~100 DEG C.

Further, the selection process temperature of warm area 2 be 30~150 DEG C, more preferable 50~120 DEG C, more preferable 60~80 ℃。

Further, 30~200 DEG C of the selection process temperature of warm area 3, more preferable 60~150 DEG C, more preferable 80~120 ℃。

Further, pickling, alkali cleaning, water washing operations are completed in the warm area of post-processing unit, can be matched using 3 warm areas It closes and completes, the post-processing operation that one or two warm area individually completes pickling, alkali cleaning, washing can also be only used.For example, will The crude product obtained after vacuum processing flows into warm area 4 with water using constant flow pump, and crude product is formed with water after warm area 4 comes into full contact with Weakly acidic solution is matched can remove acid instability impurity and metal cation after temperature appropriate, at the same time, properly The lye of concentration and dosage enters warm area 5 under constant current pumping action, so that the solution obtained in warm area 4 is become alkalinity, to complete alkali Operation is washed, the solution after alkali cleaning completes water-oil separating through oil water separator, and oil phase enters warm area 6, water phase discharge or recovery, Oil water separator is the continuous oily water separating equipment known to those skilled in the art.Similarly, when oil phase enters warm area 6, water Wash water enters warm area 6 under constant current pumping action and come into full contact with completing water washing operations with oil phase.Equally, pickling, alkali cleaning It can be integrated into an independent warm area with water washing operations to be completed.

Further, integrated continuous flow reactor post-processing unit includes at least one warm area, it is preferred that after described Processing unit includes 3 warm areas：Warm area 4, warm area 5 and warm area 6.

Further, 30~200 DEG C of 4 selection process temperature of warm area, more preferable 50~180 DEG C, more preferable 60~150 DEG C.

Further, 30~200 DEG C of 5 selection process temperature of warm area, more preferable 50~180 DEG C, more preferable 60~150 DEG C.

Further, 30~200 DEG C of 6 selection process temperature of warm area, more preferable 50~180 DEG C, more preferable 60~150 DEG C.

Further, the product that warm area 6 obtains after handling completes water-oil separating through oil water separator, and reactor is discharged in water phase Or apply mechanically, oil phase enters thin film evaporator or operation is dried in molecular distillation evaporator, obtains final finished.

Further, 30~200 DEG C of the selection process temperature of thin film evaporation, more preferable 50~180 DEG C, more preferable 60~ 150℃。

Further, in order to enable continuous flow reactor to be applicable in more continuous flow manufacturing conditions, reactor Match more functional unit, correspondingly, also has more warm area quantity, the warm area quantity of actual selection will be according to different Reaction condition is matched accordingly, when identical there are continuous warm area temperature, can be considered the same warm area, such as 4 He of warm area When 5 temperature of warm area is identical, the two can be integrated into new warm area 4, then it is 5 warm areas, warm area that integrated reactor is practical at this time 1, warm area 2, warm area 3, new warm area 4 (warm area 4+ warm areas 5) and warm area 5, other and so on.

Further, continuous flow production technology is due to productive prospecting rapidly and efficiently, ensureing that product is stable and receives Under the premise of rate, entire production process can be produced under temperature condition more higher than current technique, under the high temperature conditions, It is apparent that temperature is higher, reaction can be faster, this also promotes the production efficiency of continuous flow production technology, the mutual shadow of the two simultaneously It rings.

Further, TCPP is produced using integrated continuous flow reactor, needs strictly to match feed rate, material ratio Example, catalyst amount, reactor reaction device module or reactor module group quantity, reactor module or reactor module group with not With the collocation between warm area.Such as when low content catalyst under conditions of high flow rate, reactor module or reactor module group quantity When accordingly increasing, but the temperature of warm area being consolidated to sufficiently high, can the quantity of module group can reduce again；Correspondingly, when It, can be in higher flow rate, less reactor module or reactor module group and more low temperature relatively when using high catalyst dosage Degree is lower to carry out.TCPP can decompose under prolonged hot conditions, this is warm area number of modules well known to those skilled in the art And the matching of temperature, flow is very suitable, and TCPP could be made there was only several minutes or even several seconds in high temperature section residence time, Product is reduced to the greatest extent to lose caused by decomposition.Matching between each technological parameter and equipment is quite stringent but whole Body matching condition and quite flexible, only match suitable technological parameter and appointed condition, by integrated continuous flow reactor Continuous flow production is can be only achieved, while so that the service efficiency of integrated continuous flow reactor is reached maximum, reaches saving production Time reduces waste water, improves the purpose of product quality and finished product stability.The simple module for using reactor, module group are not The purpose of the present invention and effect can be reached.

Further, reactor module is arranged in pairs or groups multiple individual warm areas, and temperature can be identical in production process, can not also Together, so that continuous flow reactor is can be suitably used for more feed rates, catalyst amount, alkali cleaning, washing conditions, form independent work( Can unit, between each functional unit can series winding or and even by way of connect in the reactor.Matching in this way, Make continuous flow production technology more flexibility, has stronger applicability for different working conditions.

The present invention compared with the prior art, has the beneficial effect that：

1. the present invention provides a kind of completely new TCPP Total continuity stream production technologies, a kind of completely new TCPP has been made for the first time The content of product, acid value stabilization and aldehyde type impurities is 0, acid value (mg KOH/g)≤0.1, moisture content (wt.%)≤0.1, color and luster (APHA)≤50, (25 DEG C, mPas) of viscosity is 50-80.TCPP products produced by the present invention can also be free of catalyst and correspond to Metal cation, so that TCPP product qualities is mentioned and be obviously improved.

2. the present invention realizes the Total continuity stream production of TCPP for the first time, creatively the stage of reaction and post-processing stages are made It is carried out continuously, incessantly for an integrated artistic, raw material continuously enters reactor feed mouth, in reactor outlet The TCPP finished products for meeting commercial standard are continuously obtained, realizes and quickly prepares high quality tricresyl phosphate (the chloro- 2- propyl of 1-) Ester (TCPP) finished product makes TCPP prepare and realizes Total continuity stream production technology by integrated reaction technique.Compared with the prior art, originally The reaction time of invention greatly shortens, and production efficiency is greatly improved.The production technology of the present invention is totally different from existing skill Reaction member and post-processing unit, are integrated into the production technology of complete set by the technique of art, (10 minutes in a short time It is interior) finished product for meeting commercially available industrial goods standard is directly made, realize high quality, efficient production.

3. the production technology of the present invention is safe efficient, obtained TCPP final product qualities are very high, and stability is more preferable, store up for a long time Deposit no sour regurgitation.

4. the present invention can substantially reduce post-processing water consumption, that is, the generation of waste water is reduced, the phosphorus content in waste water also has bright Aobvious decline reduces the cost of wastewater treatment, keeps the production of TCPP more economical, environmentally friendly.

5. the production technology safety of the present invention has obtained significant increase.Since continuous flow reactor is with relatively small Liquid holdup and excellent heat-transfer character, in addition shorter reaction time (within 10 minutes) so that the technical process is safer. The wherein described reactor liquid holdup refer to when operation reaches stationary state, the reaction mass that has in any moment reactor it is total Volume.

6. the integrated continuous flow reactor volume that the present invention uses is small, floor space is small, has greatly saved workshop use Ground and cost.

Description of the drawings

Fig. 1 continuous flow production technology artworks of the present invention；

The schematic diagram of Fig. 2 integrated continuous flow reactors of the present invention.

Specific implementation mode

Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate this hair It is bright rather than limit the scope of the invention.In addition, it should also be understood that, after having read present disclosure, ordinary skill Personnel can make various changes or modifications the present invention, these identical or corresponding forms equally fall within right appended by the application and want Seek book limited range.

Following abbreviations are used in embodiment：

POCl₃：Phosphorus oxychloride

PO：Propylene oxide

AlCl₃：Alchlor

TiCl₄：Titanium tetrachloride

ZnCl₂：Zinc chloride

MgCl₂：Magnesium chloride

FeCl₃：Iron chloride

NaOH：Sodium hydroxide

KOH：Potassium hydroxide

Na₂CO₃：Sodium carbonate

NaHCO₃：Sodium bicarbonate

K₂CO₃：Potassium carbonate KHCO₃：Saleratus

Concentration in the embodiment of the present invention is mass concentration, it should be noted that in actual production (including laboratory, In pilot scale, actual production process) used in reaction substrate, catalyst have ± 2 percentage points mass concentration deviation；Warm area Temperature has ± 3 DEG C of deviation；Production time has the deviation of ± 5s.As depicted in figs. 1 and 2, by the raw material 1 containing catalyst (phosphorus oxychloride containing catalyst), raw material 2 (propylene oxide), 3 (water of material 1 (soda-wash water), material 2 (aqueous slkali) and material Wash water) with constant flow pump successively deliver into integrated continuous flow reactor, sequentially enter in warm area 1 to warm area 3, the reaction was complete； Outflow 3 reaction solution of warm area enters vacuum buffer tank and sloughs remaining PO, then continuously enters warm area 4, warm area 5 and warm area 6 into Row post-processing, the product for handling completion carry out film dehydration operation, finally obtain the finished product of high quality.Wherein, 1 generation of feed rate The feed rate of table raw material 1, feed rate 2 represent the feed rate of raw material 2, and feed rate 3 represents the feed rate of material 1, Feed rate 4 represents the feed rate of material 2, and feed rate 5 represents the feed rate of material 3.Wherein, soda-wash water refers to slightly producing Product add the water being added to before lye in reactor；Washing water refers to the water being added to after alkaline cleaning procedure in reactor.

Wherein, T1 represents the time of the stage of reaction, T2 represent vacuum removal residual epoxide propane (PO) impurity when Between, T3 represents the time of continuous washing and continuous liquid separation, and T4 represents the time of continuous drying dehydration.

Aldehyde material detects：The content that aldehyde type impurities is measured using GC-External Standard method, to detect 2- methyl alkene valerals For, illustrate specific detection method：

Draw standard curve：The accurate 2- methyl alkene valeral standard items for weighing certain mass, solvent is made using anhydrous propanone, It is several (being not less than 3 samples) that it is configured to standard solution of the content between 0.02ppm-0.2ppm respectively.Pass through gas-chromatography Analysis obtains the corresponding data of different content and peak area under certain condition, draws standard curve：

Y=kX+b.

In above formula, the content of aldehyde, ppm in Y-sample introduction；

K-slope of standard curve；

X-peak area；

B-standard curve intercept.

Sample measures：Accurate weighing 0.1000g TCPP samples are added in 10ml anhydrous propanones, concussion to being completely dissolved, Sample introduction is analyzed.It brings peak area data into calibration curve formula and obtains the aldehyde of sample introduction TCPP.Practical aldehyde in TCPP For 100Y (ppm).

The not sour regurgitation refers to that TCPP finished product acid values do not change, particularly, the acid value (acid of TCPP finished products Value) acid value is constant during storage, transport or downstream user use.Acid value measuring uses ASTM D974-2012 In method, concrete operations are as follows：

The sample of about 10-15g is weighed, it is accurately weighed, it is placed in 250ml conical flasks.30ml absolute ethyl alcohols are added, until sample It is completely dissolved, 0.5ml phenolphthalein indicators is added, shake to colourless homogeneous transparent.It is instilled to presentation blush with KOH standard solution, And kept for half a minute colour-fast, as titration end-point.

Same method is not added with sample and does blank test.

Acid value calculates as follows：

X=(V₁-V₂)·C/m

In above formula, the acid value of X-sample, mg KOH/g；

V₁The dosage of KOH standard solution, ml when-sample titrates；

V₂The dosage of KOH standard solution, ml when-blank titration；

The concentration of C-KOH standard solution, g/L；

The quality of m-sample, g.

The not sour regurgitation refers to that TCPP finished product acid values do not change, particularly, the acid value (acid of TCPP finished products Value) acid value is constant during storage, transport or downstream user use.Acid value measuring uses ASTM D974-2012 In method, concrete operations are as follows：

The sample of about 10-15g is weighed, it is accurately weighed, it is placed in 250ml conical flasks.30ml absolute ethyl alcohols are added, until sample It is completely dissolved, 0.5ml phenolphthalein indicators is added, shake to colourless homogeneous transparent.It is instilled to presentation blush with KOH standard solution, And kept for half a minute colour-fast, as titration end-point.

Same method is not added with sample and does blank test.

Acid value calculates as follows：

X=(V₁-V₂)·C/m

In above formula, the acid value of X-sample, mg KOH/g；

V₁The dosage of KOH standard solution, ml when-sample titrates；

V₂The dosage of KOH standard solution, ml when-blank titration；

The concentration of C-KOH standard solution, g/L；

The quality of m-sample, g.

Further, it is described in order to it is simple and quick detect finished product whether sour regurgitation and sour regurgitation degree, can be by making It is characterized and is embodied with the method for burn-in test, the specific method is as follows：Take 60gTCPP samples to the aging bottle of 60ml volumes In, it is put into after being sealed in the baking oven of 100 DEG C of constant temperature and keeps the temperature 3h, front and back comparison acid value variation.If acid value does not change, Illustrate not sour regurgitation.

The residual of the corresponding metal cation of catalyst is detected using ICP-OES 7000DV instruments, and specific method is such as Under：

Drawing curve：The standard substance for accurately weighing metallic element to be measured uses certain density HNO₃Match respectively It is several that standard solution of the content between 1ppm-100ppm is made；The blank solution for separately preparing same acidity is a.Pass through instrument Analysis obtains the spectral absorption intensity data of the metallic element standard solution of various concentration, draws working curve：

I=AC

In above formula, I-metallic element spectral absorption intensity；

A-related coefficient；

C-metallic element concentration.

Sample treatment and measurement：The TCPP samples of accurate weighing certain mass, using Muffle furnace ashing processing to it is organic at Divide and decomposes completely；Use certain density HNO₃Solution is shifted to ash content dissolution process, after depickling and is determined using 100ml volumetric flasks Hold.It tests and analyzes to obtain the spectral absorption intensity I of element by instrument, substitutes into working curve and obtain the dense metal of sample after constant volume Concentration of element C, and then calculate metal cation content therein according to TCPP sample qualities are weighed.

It can be seen that, integrated continuous flow technique of the present invention has apparent on technique total time from embodiment Progress, i.e., shortened within 10 minutes from 10 several hours of prior art.Meanwhile from embodiment 11 and 12 as it can be seen that putting Yield does not change after extensive, and the production time does not also obviously increase, and illustrates that enlarge-effect is not present in the present invention.

Embodiment：

Comparative example 1：TCPP crude products are prepared by continuous flow production technology, after being carried out using intermittent industrialized mode The embodiment of processing

500kg TCPP crude products are directly connect from integrated continuous flow reactor using the working condition of embodiment 5 Go out, is post-processed without using reactor.The crude product is transferred in 2000 liters of reaction kettles with stirring, it is then public using 17 The NaOH aqueous solutions and 500 kg of water of jin 30%, alkali cleaning 2 hours at 75 DEG C reuse 500 kilograms after standing 1 small layered Water washing 2 hours, stand hour, thin film evaporation completes dehydrating operations at 110 DEG C.Finished product acid value 0.03mgKOH/g, aging Acid value 0.05mgKOH/g afterwards.2- methyl alkene valeral contents 0.6ppm.

Comparative example 2：TCPP crude products are prepared using intermittent industrial method, after being carried out using continuous stream mode The embodiment of reason

Take 500 kilograms of TCPP crude products for industrially producing at present, using the present invention integrated continuous flow reactor into Row post-processing operation.Crude product flow 80L/h, 1 flow 25L/h of material, material 2 are 8% sodium hydrate aqueous solution, and material 2 flows Measure 10.5L/h, 3 flow 31.6L/h of material.The temperature that material flows through reactor is 130 DEG C.Finished product is taken to carry out after dehydration Analysis：Finished product acid value 0.01mgKOH/g, acid value 0.03mgKOH/g after aging.2- methyl alkene valeral contents 33ppm.

Comparative example 3：Industrial batch autoclave TCPP production technologies at present

3000 kilograms of phosphorus oxychloride and 9 kg catalyst alchlors are put into 8 cubes of kettles, and 60 are warming up under stirring DEG C, then start that 3400 kilograms of rings third are added dropwise, is added dropwise 5 hours, then keeps the temperature 5 hours between 60 to 70 DEG C.After reaction PO about 30min are drawn under vacuum.The then NaOH and 3000 kg of water using 100 kilogram 30%, alkali cleaning 2 hours at 75 DEG C, It stands and reuses 3000 kilograms of water washing 2 hours after 1 small layered, stand hour, thin film evaporation completes dehydration at 110 DEG C Operation.Finished product acid value 0.02mgKOH/g, acid value 0.06mgKOH/g after aging.2- methyl alkene valeral contents 15ppm.

Above comparative example explanation only uses the reaction of continuous flow, but without using the post-processing of continuous flow, obtain at Product still will appear sour regurgitation；Correspondingly, it does not use continuous flow to react, but only uses continuous flow and post-processed, obtained finished product The features such as still will appear sour regurgitation and containing aldehyde type impurities.

Claims (10)

1. a kind of tricresyl phosphate（The chloro- 2- propyl of 1-）Ester（TCPP）Finished product, which is characterized in that the content of its aldehyde type impurities is 0, acid value (mg KOH/g)≤0.1, moisture content (wt. %)≤0.1, color and luster (APHA)≤50, (25 DEG C, mPas) of viscosity are 50- 80。

2. tricresyl phosphate according to claim 1（The chloro- 2- propyl of 1-）Ester（TCPP）Finished product, it is characterised in that the TCPP Finished product does not contain 2- methyl alkene valerals.

3. according to claim 1-2 any one of them tricresyl phosphates（The chloro- 2- propyl of 1-）Ester（TCPP）Finished product, which is characterized in that TCPP finished products acid value≤0.07mgKOH/g, preferred acid number≤0.05mgKOH/g, more preferable acid value≤0.01mgKOH/g.

4. according to claim 1-2 any one of them tricresyl phosphates（The chloro- 2- propyl of 1-）Ester（TCPP）Finished product, which is characterized in that The moisture（wt,%）≤ 0.07%, preferably moisture（wt,%）≤0.05%.

5. according to claim 1-2 any one of them tricresyl phosphates（The chloro- 2- propyl of 1-）Ester（TCPP）Finished product, which is characterized in that (25 DEG C, mPas) of the viscosity is 65-72mPa.s, preferably 68-70 mPa.s.

6. according to claim 1-2 any one of them tricresyl phosphates（The chloro- 2- propyl of 1-）Ester（TCPP）Finished product, which is characterized in that The color and luster (APHA)≤30, preferably color and luster (APHA)≤20.

7. a kind of tricresyl phosphate（The chloro- 2- propyl of 1-）Ester（TCPP）The Total continuity stream production technology of finished product, which is characterized in that described Production technology carries out in integrated continuous flow reactor, and the production technology includes the stage of reaction and post-processing stages, institute The stage of reaction and post-processing stages stated carry out continuously, incessantly, in the feed inlet of the integrated continuous flow reactor It is uninterrupted that propylene oxide, phosphorus oxychloride, catalyst, lye, water is added, the integrated continuous flow reactor discharge port not between It is disconnected to obtain tricresyl phosphate（The chloro- 2- propyl of 1-）Ester（TCPP）Finished product, TCPP production technologies total time≤10 minute.

8. Total continuity stream production technology according to claim 7, which is characterized in that the integrated continuous flow reactor Including reaction member and post-processing unit, the reacted unit of raw material propylene oxide, phosphorus oxychloride, catalyst completes the stage of reaction, Post-treated unit obtains TCPP finished products again.

9. a kind of integrated continuous flow reactor for the Total continuity stream production technology being exclusively used in described in claim 7 or 8, feature It is, the integrated continuous flow reactor includes one or more functions unit.

10. a kind of integrated continuous flow reactor for the Total continuity stream production technology being exclusively used in described in claim 7 or 8, special Sign is that it includes at least one functional unit, Mei Gegong that the integrated continuous flow reactor, which uses having unit structure, reactor, Energy unit includes at least one warm area, and each functional unit includes independently one or more reactor module or reaction Device module group is wherein serially connected between each warm area of functional unit, one or more reactor reactions in each functional unit Device module or reactor module group are connected in series or in parallel.