CN104974062A - TDI purification process of zone melting method - Google Patents
TDI purification process of zone melting method Download PDFInfo
- Publication number
- CN104974062A CN104974062A CN201510368845.0A CN201510368845A CN104974062A CN 104974062 A CN104974062 A CN 104974062A CN 201510368845 A CN201510368845 A CN 201510368845A CN 104974062 A CN104974062 A CN 104974062A
- Authority
- CN
- China
- Prior art keywords
- zone
- tdi
- melting
- district
- certain
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention relates to the technical field of melted crystallization refining, and specifically relates to a 2,4-TDI purification process of a zone melting method. The process comprises the following steps: purifying a TDI-80 raw material, carrying out recrystallization until the TDI purity reaches a certain degree; putting the re-crystallized TDI into a zone melting tube until a certain height is reached; curing the TDI, moving the zone melting tube from top to bottom at a certain speed, wherein the moving speed of the zone melting tube is controlled by a speed modulator; adjusting the heating temperature of a melting zone with a certain area in the zone melting tube through a heating apparatus and controlling the temperature of a cold zone in the zone melting tube by a super low temperature thermostatic bath so as to achieve a certain temperature difference between the heating temperature and the cold zone temperature, sampling TDI in different positions of the zone melting tube, and analyzing the purity; wherein the zone melting speed is 10 mm/h during the zone melting process, the melting zone length is 15 mm, the temperature difference is 50 DEG C, the melting zone moves upwards, after 6 times of zone melting, the TDI yield can reach at least 60%, and the purity can reach 98.5% or more.
Description
Technical field
The present invention relates to fusion-crystallization technical field of refinement, be specifically related to a kind of zone melting process purifying TDI process.
Background technology
At present, urethane is the world six one of synthetic materials with development prospect greatly.It has wear-resisting, low temperature resistant, the function such as oil resistant and resistance to ozone, achieves fast development in recent years, be widely used in porous plastics, sizing agent, elastomerics, coating and fiber etc. in China.And the isocyanic ester that in polyurethane industrial, consumption is maximum mainly tolylene diisocyanate (C9H6N2O2 is called for short TDI) and diphenylmethanediisocyanate (being called for short MDI).Wherein the consumption of TDI is huge, and domestic market consumption reaches more than 300,000 tons/year.TDI mainly contains two kinds of isomerss: 2,4 toluene diisocyanate (2,4-TDI) and 2,6-tolylene diisocyanate (2,6-TDI).According in TDI product, the difference of 2,4-TDI and 2,6-TDI Isomer ratio, TDI industrial goods can be divided into three kinds of specification TDI-100, TDI-80/20, TDI-65/35, the content of numeral 2,4-TDI above.In three kinds of products, TDI-100 added value is the highest, and its price is about more than 2 times of other two kinds of specification products.But up to the present, the domestic device also not producing TDI-100.
Fusion-crystallization purification techniques is difference according to zero pour between separate substance and realizes the method for separating substances and purification, has that product purity is high, energy consumption is low, does not need to add other solvents, the features such as environmental pollution is little.Fusion-crystallization can be divided into following three classes by operating method: laminar crystallization, suspension crystallization and zone melting.Current laminar crystallization and floated crystallization all realize industrialization in separating organic matters field, such as 1-naphthols, dimethylbenzene, refined naphthalene, and zone melting process be mainly used in metallic substance purification, its metal purity can reach more than 99.999%, and the bibliographical information of purifying to organism is less.
Summary of the invention
The object of the invention is to solve the problem, a kind of zone melting process purifying TDI process is provided, can solves the problem.
The present invention's adopted technical scheme that solves the problem is:
A kind of zone melting process purifying TDI process, carry out successively according to following steps:
Step one, purified by TDI raw material, after recrystallization, the purity of TDI reaches certain degree;
Step 2, test tube is melted in the TDI loading area after recrystallization, load certain height;
Step 3, solidified by TDI, district melts test tube and moves from the top down, and district melts test tube and moves according to certain rate travel, and the rate travel that test tube is melted in described district is controlled by speed regulator;
Step 4, melted the Heating temperature in vitro a certain size melting zone by heating unit regulatory region, the cold-zone temperature in vitro melting zone is melted by super low temperature thermostat bath control region, certain temperature head is formed between Heating temperature and cold-zone temperature, after district's clinkering bundle, get the TDI that different positions in test tube is melted in district, analyze its purity.
Preferably, it is 90.1% that described step one moderate purity reaches certain degree.
Preferably, height certain in described step 2 is 100mm.
Preferably, rate travel certain in described step 3 is 10mm/h.
Preferably, temperature head certain in described step 4 is 50 DEG C, and in described step 4, a certain size melting zone is 15mm.
Preferably, described district melts and in vitro adopts region straight up, melting zone to carry out district and melt, and the molten number of times in district is 6 times.
The invention has the beneficial effects as follows: the zone melting process purifying TDI that the present invention proposes is a method completely newly preparing TDI-100.Zone melting is as the ultrapure refinement technique of one, and energy consumption in traditional rectification method purifying technique can be avoided large in for purifying TDI process, resolution is limited, and in products obtained therefrom, the purity of 2,4-TDI is not very high shortcoming.Melt in district in process, finally determine to adopt the district of 10mm/h to melt speed, the melting zone of 15mm, the temperature difference of 50 DEG C, the condition that melting zone moves up, after 6 times are melted in district, the yield of 2,4-TDI reaches more than 60%, and product purity reaches more than 98.5%.
Accompanying drawing explanation
Fig. 1 is the chromatographic fractionation figure of TDI after the present invention's three recrystallizations;
Fig. 2 is that melting zone of the present invention rate travel is on the impact of purity;
Fig. 3 is the impact of temperature head of the present invention on purity;
Fig. 4 is that melting zone of the present invention size is on the impact of purity;
The impact of direction on purity is melted in Tu5Shi district of the present invention;
Tu6Shi district of the present invention heat number is on the impact of purity.
Embodiment
A kind of zone melting process purifying TDI process of the present invention, carry out successively according to following steps:
Step one, purified by TDI raw material, after recrystallization, the purity of TDI reaches certain degree;
Step 2, test tube is melted in the TDI loading area after three recrystallizations, load certain height;
Step 3, solidified by TDI, district melts test tube and moves from the top down, and district melts test tube and moves according to certain rate travel, and the rate travel that test tube is melted in described district is controlled by speed regulator;
Step 4, melted the Heating temperature in vitro a certain size melting zone by heating unit regulatory region, the cold-zone temperature in vitro melting zone is melted by super low temperature thermostat bath control region, certain temperature head is formed between Heating temperature and cold-zone temperature, after district's clinkering bundle, get the TDI that different positions in test tube is melted in district, analyze its purity.As Fig. 1.
Fig. 2 is the effect diagram of rate travel to product purity in melting zone, has investigated under different districts melts speed respectively, and the purity of sample is along the distribution situation of sample rod.As can be seen from the figure, sample is on a declining curve along the purity profile of sample rod, and the purity of the initiating terminal of sample rod is higher than raw material, and the purity of afterbody is lower than raw material, and declare area scorification has certain purification effect to TDI; When other conditions are identical, along with the rate travel in melting zone reduces, the purity of sample rod initiating terminal is higher, and the purity of afterbody is lower.This is because lower melting zone rate travel is conducive to the transmission of impurity between melting zone and crystal plane in melting zone, be more conducive to the partition equilibrium of impurity between crystal plane and melting zone, complete a district simultaneously and melt the also corresponding increase of required time.When melting zone rate travel is infinitely small, impurity in process is melted in district will close to its equilibrium distribution, but overlong time used is melted in district, cannot practical application.As shown in Figure 3, when to melt speed be 10.4mm/h in district, the purity of sample rod initiating terminal reaches 98.6%, meet the standard (98.5%) of TDI-100, and when to melt speed be 5mm/h in district, refining effect is not obvious especially compared with 10.4mm/h, so consider time and refining effect, district melts rate selection 10mm/h and is advisable.
Whether the temperature head in Zone melting purifying device between water cooler and well heater successfully plays vital effect for zone-refine.Due to the physical property of TDI, can be polymerized when 50 DEG C, so the temperature of well heater controls at 45 DEG C, the temperature changing water cooler investigates the impact of temperature head on product purity.As can be seen from Figure 3, along with the increase of temperature head, the purity of the initiating terminal of sample rod presents increase trend.This is because the temperature head of melting zone and water cooler is larger, be more conducive to the diffusion of molecule in melting zone, increase the mass transfer force between crystalizing interface and melting zone; In addition, large temperature head can reduce the probability that structural subcooling phenomenon occurs.Structural subcooling phenomenon refers to material when solidifying, and form the phenomenon at the interface that is uneven, this phenomenon significantly can reduce separating effect.As shown in Figure 4, temperature head is larger, and refining effect is better, adopts temperature head to be that 50 DEG C of zone melting purification processes for TDI are comparatively suitable.
As shown in Figure 4, for melting zone size is on the impact of product purity, investigate the impact of melting zone on product purity that 5mm, 10mm, a 15mm are melted in district respectively.A lot of scholar has done a large amount of theoretical investigationes to the impact of melting zone size.On the one hand, when melting zone is larger, for identical impurity, the impurity that can hold in melting zone is more, and the number of times needing district molten is just less comparatively speaking, otherwise if melting zone is less, the number of times needing district molten is more.As can be seen from the figure, when speed and the temperature difference one timing are melted in district, obtained product purity is melted apparently higher than little melting zone in large melting zone district, and the zone-refine therefore for TDI adopts the melting zone of 15mm proper.
In general, horizontal than vertical weak effect for organic zone melting.Therefore the vertical zone melting that the present invention adopts, investigate melting zone straight up and straight down zone melting respectively.As shown in Figure 5, when melting zone moves up, the purity when purity of the initiating terminal product of sample rod moves down higher than melting zone.Because melt in district in process, due to the effect of gravity, the melt in melting zone has the trend moved downward, when melting zone moves up, crystalizing interface is positioned at the lower interface in melting zone, and now melting zone contacts with crystalizing interface well, and the mass transfer between crystalizing interface and melting zone is good; When melting zone moves down, crystalizing interface is positioned at the upper interface in melting zone, and crystal plane and melting zone loose contact, be unfavorable for the mass transfer in crystal plane and melting zone.Therefore select melting zone zone melting effect straight up better.
District's heat number is the important factor affecting refining effect.For same impurity, when other conditions are identical, district's heat number is more, and the amount of removing of impurity is more, but when Impurity Distribution reaches capacity distribution, increases the distribution that district's heat number also can not affect impurity in time.As shown in Figure 6, for district's heat number is on the impact of product purity.As can be seen from Figure 6, along with the increase of district's heat number, the purity of sample rod middle portion improves gradually.When district's heat number reaches 6 times, the purity of the first half of sample rod is all greater than (or equaling) 98.5%, and yield reaches more than 60%.
The technician of the industry should understand; the present invention is not restricted to the described embodiments; what describe in above-described embodiment and specification sheets just illustrates principle of the present invention; without departing from the spirit and scope of the present invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the claimed scope of the invention.Application claims protection domain is defined by appending claims and equivalent thereof.
Claims (6)
1. a zone melting process purifying TDI process, is characterized in that: carry out successively according to following steps:
Step one, purified by TDI raw material, after recrystallization, the purity of TDI reaches certain degree;
Step 2, test tube is melted in the TDI loading area after recrystallization, load certain height;
Step 3, solidified by TDI, district melts test tube and moves from the top down, and district melts test tube and moves according to certain rate travel, and the rate travel that test tube is melted in described district is controlled by speed regulator;
Step 4, melted the Heating temperature in vitro a certain size melting zone by heating unit regulatory region, the cold-zone temperature in vitro melting zone is melted by super low temperature thermostat bath control region, certain temperature head is formed between Heating temperature and cold-zone temperature, after district's clinkering bundle, get the TDI that different positions in test tube is melted in district, analyze its purity.
2. a kind of zone melting process purifying TDI process according to claim 1, is characterized in that: it is 90.1% that described step one moderate purity reaches certain degree.
3. a kind of zone melting process purifying TDI process according to claim 1, is characterized in that: height certain in described step 2 is 100mm.
4. a kind of zone melting process purifying TDI process according to claim 1, is characterized in that: rate travel certain in described step 3 is 10mm/h.
5. a kind of zone melting process purifying TDI process according to claim 1, it is characterized in that: temperature head certain in described step 4 is 50 DEG C, in described step 4, a certain size melting zone is 15mm.
6. a kind of zone melting process purifying TDI process according to Claims 2 or 3 or 4 or 5, is characterized in that: described district melts and in vitro adopts region straight up, melting zone to carry out district and melt, and the molten number of times in district is 6 times.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510368845.0A CN104974062B (en) | 2015-06-30 | 2015-06-30 | A kind of zone melting method purifies TDI processes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510368845.0A CN104974062B (en) | 2015-06-30 | 2015-06-30 | A kind of zone melting method purifies TDI processes |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104974062A true CN104974062A (en) | 2015-10-14 |
| CN104974062B CN104974062B (en) | 2017-07-21 |
Family
ID=54271079
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510368845.0A Active CN104974062B (en) | 2015-06-30 | 2015-06-30 | A kind of zone melting method purifies TDI processes |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104974062B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232276A (en) * | 2018-11-13 | 2019-01-18 | 蚌埠医学院第附属医院 | A method of using microwave oven apparatus area smelting refinement p-phenylenediamine |
| CN109970604A (en) * | 2019-04-25 | 2019-07-05 | 青岛科技大学 | A kind of technique purifying 2,4 toluene diisocyanate |
| CN110734577A (en) * | 2019-11-04 | 2020-01-31 | 安徽建筑大学 | method for reducing heavy metal content in ABS plastics |
| CN111413294A (en) * | 2020-03-31 | 2020-07-14 | 西北农林科技大学 | Method for rapidly detecting wax in sunflower seed oil |
| CN112357894A (en) * | 2020-11-17 | 2021-02-12 | 昆明理工大学 | Crude tellurium crystallization purification method |
| CN115196656A (en) * | 2022-08-26 | 2022-10-18 | 华中科技大学鄂州工业技术研究院 | CsBr purification method |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52111543A (en) * | 1976-03-12 | 1977-09-19 | Orient Chemical Ind | Method of separation of tar component from crude tolylenediisocyanate |
| US4296612A (en) * | 1980-06-18 | 1981-10-27 | Chicago Bridge & Iron Company | Freeze exchanger with removable tube liner |
| CN1792406A (en) * | 2005-11-25 | 2006-06-28 | 四川大学 | Equipment for preparing high pure organic matter by fusion-crystallization method |
| CN101003498A (en) * | 2007-01-09 | 2007-07-25 | 宁波万华聚氨酯有限公司 | Method for preparing 4,4'- diphenylmethane diisocyanate with prolonged memory cycle |
| EP2080545A1 (en) * | 2008-01-18 | 2009-07-22 | NIRO Process Technology B.V. | Method for solid liquid separation |
| CN101525283A (en) * | 2009-03-23 | 2009-09-09 | 中国计量科学研究院 | Zone melting purification device and method of purifying phenylformic acid by adopting same |
| CN101928236A (en) * | 2009-11-05 | 2010-12-29 | 甘肃银达化工有限公司 | Method for separating TDI monomer with different isomerization rates |
| CN102171180A (en) * | 2008-10-06 | 2011-08-31 | 亨茨曼国际有限公司 | Process for the simultaneous production of different mixtures of diisocyanate isomers of the diphenylmethane series |
-
2015
- 2015-06-30 CN CN201510368845.0A patent/CN104974062B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS52111543A (en) * | 1976-03-12 | 1977-09-19 | Orient Chemical Ind | Method of separation of tar component from crude tolylenediisocyanate |
| US4296612A (en) * | 1980-06-18 | 1981-10-27 | Chicago Bridge & Iron Company | Freeze exchanger with removable tube liner |
| CN1792406A (en) * | 2005-11-25 | 2006-06-28 | 四川大学 | Equipment for preparing high pure organic matter by fusion-crystallization method |
| CN101003498A (en) * | 2007-01-09 | 2007-07-25 | 宁波万华聚氨酯有限公司 | Method for preparing 4,4'- diphenylmethane diisocyanate with prolonged memory cycle |
| EP2080545A1 (en) * | 2008-01-18 | 2009-07-22 | NIRO Process Technology B.V. | Method for solid liquid separation |
| CN102171180A (en) * | 2008-10-06 | 2011-08-31 | 亨茨曼国际有限公司 | Process for the simultaneous production of different mixtures of diisocyanate isomers of the diphenylmethane series |
| CN101525283A (en) * | 2009-03-23 | 2009-09-09 | 中国计量科学研究院 | Zone melting purification device and method of purifying phenylformic acid by adopting same |
| CN101928236A (en) * | 2009-11-05 | 2010-12-29 | 甘肃银达化工有限公司 | Method for separating TDI monomer with different isomerization rates |
Non-Patent Citations (2)
| Title |
|---|
| 卢咏琰: "TDI熔融结晶过程研究", 《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》 * |
| 贾乃芬: "有机物纯化处理的新技术—对流结晶和区域熔融", 《辽宁化工》 * |
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109232276A (en) * | 2018-11-13 | 2019-01-18 | 蚌埠医学院第附属医院 | A method of using microwave oven apparatus area smelting refinement p-phenylenediamine |
| CN109970604A (en) * | 2019-04-25 | 2019-07-05 | 青岛科技大学 | A kind of technique purifying 2,4 toluene diisocyanate |
| CN109970604B (en) * | 2019-04-25 | 2021-03-19 | 青岛科技大学 | Process for purifying 2, 4-toluene diisocyanate |
| CN110734577A (en) * | 2019-11-04 | 2020-01-31 | 安徽建筑大学 | method for reducing heavy metal content in ABS plastics |
| CN111413294A (en) * | 2020-03-31 | 2020-07-14 | 西北农林科技大学 | Method for rapidly detecting wax in sunflower seed oil |
| CN111413294B (en) * | 2020-03-31 | 2023-03-28 | 西北农林科技大学 | Method for rapidly detecting wax in sunflower seed oil |
| CN112357894A (en) * | 2020-11-17 | 2021-02-12 | 昆明理工大学 | Crude tellurium crystallization purification method |
| CN115196656A (en) * | 2022-08-26 | 2022-10-18 | 华中科技大学鄂州工业技术研究院 | CsBr purification method |
| CN115196656B (en) * | 2022-08-26 | 2023-09-19 | 华中科技大学鄂州工业技术研究院 | CsBr purifying method |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104974062B (en) | 2017-07-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104974062A (en) | TDI purification process of zone melting method | |
| CN105316641A (en) | Coating substrate support and vacuum coating equipment | |
| CN203510196U (en) | Movable clamp frame | |
| CN204706317U (en) | A kind of painting poster cloth suspension holdfast | |
| CN104818522A (en) | Diameter adjustable liquid bridge generator | |
| CN102285658B (en) | Multistage fully thermally coupled rectification production device and process method for preparing ultra-pure trichlorosilane | |
| CN206864141U (en) | A kind of billboard of installing frame dimension adjustable | |
| CN203253529U (en) | Conveying belt de-ironing separator | |
| CN205443407U (en) | Draw ann double flute cooling system greatly | |
| CN202594950U (en) | Suspension type tin bath water package adjusting device | |
| CN203443841U (en) | Crucible support for electrothermal smelter | |
| CN2928472Y (en) | Stretching device for polymer optic fiber prefabricated stick | |
| CN203484623U (en) | System for spraying and manufacturing a plurality of amorphous alloy ribbons | |
| CN208408495U (en) | A kind of air-conditioning and cooling monocrystalline seamless copper pipe production equipment | |
| CN107619903A (en) | A kind of high efficiency feeds silk spheroidizing process | |
| CN207759613U (en) | A kind of robotically-driven material-strewing device | |
| CN203621426U (en) | Billet lifting device for continuous casting machine | |
| CN202387250U (en) | Industrial column chromatography charging frame | |
| CN204385049U (en) | A kind of suspender member of tin groove roof cover | |
| CN206824627U (en) | A kind of magnesium base alloy casting machine | |
| CN202653688U (en) | Cable sample holder | |
| CN203910922U (en) | Rotary lithium cell gasket placement device | |
| CN202987948U (en) | Intermediate tank | |
| CN214569812U (en) | Multi-head color band placing device for cable production | |
| CN219470224U (en) | Cathode substrate dezincification device |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant |