CN102585191B - Novel tower reactor and application of novel tower reactor in continuously producing polyester polyol - Google Patents
Novel tower reactor and application of novel tower reactor in continuously producing polyester polyol Download PDFInfo
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Abstract
The invention discloses a novel tower reactor and application of the novel tower reactor in continuously producing polyester polyol, and in particular relates to a multi-section bubble tower reactor. The reactor is mainly formed by nesting an outer tower and a tower core, can be applied to an esterification stage and a polycondensation stage which are used for continuous polyester polyol production, or applied to ester exchange of dicarboxylic ester and polyol, and the like. By adopting the continuous production process and device, process retention time is uniformly controlled, process heat transfer and mass transfer are enhanced, operation cost is effectively reduced, and efficient flexible production requirement is met.
Description
Technical field
The present invention relates to the application of a kind of novel tower-type reactor and continuous production of polyesters polyvalent alcohol thereof.
Background technology
Polyester polyol is normally by Dicarboxylic Acids (acid anhydrides or ester) and polyvalent alcohol (comprising glycol) condensation (or transesterify) or be polymerized by lactone and polyvalent alcohol, it is one of production PAUR main raw material, the polyester polyol of plurality of specifications and the trade mark can be by generating different polyurethane products from isocyanate reaction, be widely used in leatheroid, coating, tackiness agent etc., and the quality good or not of polyester polyol will directly affect the performance of these goods.Along with the development of Polyurethane Industry, the application of polyester polyol is also more and more extensive.
Traditional polyester polyol production technique is batch production technique at present, Du Pont, Bayer, BASF, Mitsui Takeda Chemical Co., Ltd and Fujian Xingyu Resin Co., Ltd. have all applied for Patents to batch production technique and the formula of different polyester polyols, as US 2006069175, CN 1668668, DE 102006048288, CN 101168592, DE 10223055, CN 1656140, CN 1339516, CN 201343512 etc.
In interrupter method synthesizing polyester polyvalent alcohol process, polyvalent alcohol and polycarboxylic acid (and acid anhydrides or other derivatives) carry out esterification/transesterify and polycondensation at 130～240 ℃, normal pressure steams except the water and other small molecules that generate, in the decompression of reaction later stage, remove and anhydrate and other small molecules, reaction is carried out to the direction that generates low acid number polyester polyol, and also the sustainable rare gas elementes such as nitrogen that pass into are with band water outlet and other small molecules.
Interrupter method synthesizing polyester polyvalent alcohol, although it is produced flexibly, can produce multiple trade mark polyester polyol product, but its unstable product quality, have a strong impact on the process for processing (polyester polyol is general all as chemical industry intermediate product) of subsequent product, because mass-and heat-transfer is limited, its reaction time is long especially simultaneously, and production unit quality product consumes very large in the energy and human cost.
In order to strengthen heat and mass transport, avoid residual in system of catalyzer simultaneously, Dow global technical company has developed polyester polyol semi-continuous production technique, as described in WO 02008037400, CN 101516965, polycarboxylic acid and polyvalent alcohol are carried out to esterification not adding in Autoclave in catalyzer situation, then the oligopolymer obtaining is passed through to load the fixed-bed reactor of tungstenic supported catalyst continuously, carry out the continuous polycondensation in later stage.
Continuous processing synthesizing polyester polyvalent alcohol, its constant product quality, owing to having strengthened mass-and heat-transfer, increasingly automated operation, has obviously shortened the reaction times, and production unit quality product consumes little in the energy and human cost.By rational technique and device design, continuous production device also can be produced multiple trade mark polyester polyol product simultaneously.
For the processing method of continuous synthesizing polyester polyvalent alcohol, satisfied condition is very important below:
1, suitable technology controlling and process and device structure, avoid undesirable side reaction to occur;
2, as quickly as possible except anhydrating and other small molecules, the molecular balance of main reaction is moved right;
3, optimum synergistic heats up and controls with pressure operation, so that esterification and/or transesterification reaction and polycondensation complete as far as possible effectively;
4, esterification and/or transesterification reaction and polycondensation are reaction of high order, and the reactor types that approaches plug flow is paid the utmost attention in the selection of process device.
Only by a plurality of stirring tanks that connect successively, realize unsatisfactorily these targets.Patent US 5372790 has announced a kind of vertical multi-layer stirred autoclave, although reactor approaches plug flow form, mixing of materials relies on mechanical stirring, and energy consumption is large, and mechanical seal easily leaks, and affects the stable operation of successive processes.
The upflowing polyester prepolymerization reaction still (UFFP) of DuPont company, machinery-free stirs, simple in structure, reduced investment.But in still there is more dead band in tower tray, must rely on violent bubbling self-cleaning, otherwise the serious coking of meeting, and in reactor, having higher liquid level, whole tower pressure drop is larger.Development along with process, DuPont company is applied to polyester precondensation by plate distillation column, as patent US 5786443, US 849849, CN 1137278 etc., and reactor machinery-free stirs, simple in structure, but process operation elasticity is little, and the interior residence time of reactor is relatively short, is not suitable for the continuous production of polyester polyol.
Inventa company has developed a kind of relatively intensive tower reactor, and is applied to esterification and the precondensation of polyester.Its precondensation stage has adopted multistage overflow cascade, and reactor machinery-free stirs, and simple in structure, process operation elasticity is large, but needs reactor bottom to vacuumize, and drives gas bubbling from top to bottom, realizes the abundant mixing of material.
Summary of the invention
According to deficiency of the prior art, target of the present invention is to provide a kind of machinery-free and stirs, and simple in structure, turndown ratio is large, without the Multistage tower-type reactor of outer power, and be applied to the esterification of polyester polyol quantity-produced and/or transesterify stage and polycondensation phase.
By esterification and/or the transesterification reaction of polycarboxylic acid under the existence of catalyzer and/or polycarboxylic acid derivative and polyvalent alcohol and/or polyol derivative, with polycondensation, obtain the polyester polyol product of certain acid number and molecular weight.
(i) reaction raw materials is at least one or multiple polycarboxylic acid and/or polycarboxylic acid derivative and at least one or multiple polyvalent alcohol and/or polyol derivative.
(a) polycarboxylic acid and derivative thereof comprise the organic polycarboxylic acid that has certain carbon atom and have 2～4 carboxyls, and derivative.Suitable polycarboxylic acid and derivative thereof comprise: the acid anhydrides of aliphatics polycarboxylic acid, alicyclic polycarboxylic acid, unsaturated alkyl polycarboxylic acid, aromatic polycarboxylic acid and aforementioned polycarboxylic acid and derivative thereof etc.Aliphatics polycarboxylic acid comprises: succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, SA, undecane diacid, dodecanedioic acid etc.; Alicyclic polycarboxylic acid comprises: hexahydrobenzene dioctyl phthalate, 1,3-cyclohexane diacid, Isosorbide-5-Nitrae-cyclohexane diacid etc.; Unsaturated alkyl polycarboxylic acid comprises: FUMARIC ACID TECH GRADE, maleic acid etc.; Aromatic polycarboxylic acid comprises: phthalic acid, m-phthalic acid, terephthalic acid, 1,2,4-benzene tricarboxylic acid, 1,3,5-benzene tricarboxylic acid, NDA etc.; The acid anhydrides of polycarboxylic acid comprises: maleic anhydride, Tetra hydro Phthalic anhydride, TMA etc.
(b) polyvalent alcohol and derivative thereof comprise the organic polyhydric alcohol that has certain carbon atom and have 2～4 hydroxyls, and derivative.Suitable polyvalent alcohol and derivative thereof comprise: dibasic alcohol, trivalent alcohol, tetravalent alcohol and derivative thereof etc.Dibasic alcohol comprises: ethylene glycol, glycol ether, polyoxyethylene glycol, 1,2-PD, 1,3-PD, dipropylene glycol, 1,4-butyleneglycol, neopentyl glycol, 1,6-hexylene glycol, 1,10-certain herbaceous plants with big flowers glycol, 1,3-cyclohexanedimethanol, 1,4 cyclohexane dimethanol etc.; Trivalent alcohol comprises: glycerine, TriMethylolPropane(TMP) etc.; Tetravalent alcohol comprises: tetramethylolmethane etc.
(c) polycarboxylic acid and derivative thereof and polyvalent alcohol and derivatives reaction mol ratio thereof are 1: 1～1: 4, are preferably 1: 1.03～1: 2.
(ii) catalyzer is catalyzer and the compositions thereof such as at least one or multiple titanium system, antimony system, germanium system, tin system and tungsten system.
(a) catalyzer is selected from following compounds: one or more in isopropyl titanate, tetrabutyl titanate, titanium ethylene glycolate, water-resistant solution titanium catalyst, antimonous oxide, antimony acetate, antimony glycol, germanium dioxide, dibutyl tin laurate, phospho-wolframic acid etc.
(b) one or more Titanium series catalysts in the preferred isopropyl titanate of catalyzer, tetrabutyl titanate, titanium ethylene glycolate, water-resistant solution titanium catalyst etc.
(c) catalyzer usage quantity is 10～1000ppm of raw material total mass.
The outer tower of this tower reactor forms at the bottom of being provided with tower top, the tower body of material inlet and volatiles outlet and being provided with the tower of material outlet, and Heat preservation chuck (7) is installed at the bottom of tower body and tower; Tower core is nested in outer tower, and tower core is multistage overflow bubble tower.
Reaction raw materials (1) is through being preheated to 90～260 ℃, be continuously fed into first step overflow bubble tower, material completes step by step from top to bottom reaction under 130～260 ℃ and 0.1～2 kilogram of pressure in tower reactor, by higher level's overflow bubble tower (10) overflow, through downtake (11), flow to next stage overflow bubble tower, until at the bottom of outflow reactor tower, obtain reaction product (14); The small molecules steam that in overflow bubble towers at different levels, reaction produces and the polyvalent alcohol of vaporization, by bubbling tracheae (8) bubbling from bottom to top, with the liquid material countercurrent flow flowing downward, converge step by step and tower top, without or through (2) separation of packing tower joint, obtain overhead product (3).
At the bottom of rare gas element (13) (as nitrogen, carbonic acid gas, helium etc.) can being introduced to reactor column by sparger (12), from bottom to top converge step by step, from reactor head, with other small molecules, discharge system.It suppresses polymer degradation on the one hand as shielding gas, also reduces on the other hand small molecules dividing potential drop, contributes to small molecules to remove.Pass into the rare gas element of system before contacting with polymkeric substance, be preheating to polymer temperature or higher than polymer temperature.At the bottom of simultaneous reactions device tower, can pass through sparger (16) and introduce quite and raw material 0.1～10%wt polyvalent alcohol (15), further reduce the acid number of (14).
In overflow bubble towers at different levels (10), all there is heating coil heat supply, guarantee that reaction mass is at 130～260 ℃.Overflow bubble towers at different levels (10) aspect ratio is 0.2～2, bubbling tracheae (8) connects suitable gas distributor simultaneously, the size of its overflow ducts, bubbling tracheae size, quantity and the gas distributor form connecting thereof, size all need change and change with progression, to guarantee necessary bubbling effect and suitable plate pressure drop.The residence time of overflow bubble tower materials at different levels is 5～50 minutes, and the relatively long residence time, to guarantee fully carrying out of reaction.
This tower reactor structure is as follows: reaction raw materials (1) is through being preheated to 90～260 ℃, be continuously fed into first step overflow bubble tower, material completes step by step from top to bottom reaction under 130～260 ℃ and 0.1～2 kilogram of pressure in tower reactor, by higher level's overflow bubble tower (10) overflow, through downtake (11), flow to next stage overflow bubble tower, until at the bottom of outflow reactor tower, obtain reaction product (14); The small molecules steam that in overflow bubble towers at different levels, reaction produces and the polyvalent alcohol of vaporization, from bottom to top converge and tower top step by step by bubbling tracheae bubbling.For esterification and/or transesterify elementary reaction, overhead vapor is through (2) separation of packing tower joint, most of alcohol returns to first step overflow bubble tower with phegma, most of water and other small molecules distillates (3) are discharged from tower top, after interchanger (4) is cooling, part is returned to packing tower joint (2) as phegma (6), and rest part is as waste liquid (5) discharge system; For polycondensation phase reaction, overhead vapor is directly as distillate (3) discharge system, and condensable gases can be used as and reclaims alcohol use after condensation.
This Multistage tower-type reactor, not only for continuous production of polyesters polyvalent alcohol, can be applied to the pre-collecting process such as polymeric amide or polycarbonate simultaneously.
Accompanying drawing explanation
Fig. 1 represents the first distortion of the tower staged reactor of the present invention;
Fig. 2 represents the second distortion of the tower staged reactor of the present invention;
Fig. 3 represents the bubble tray of the tower staged reactor counter-current flow of the present invention
Embodiment
Provide following examples to illustrate the present invention, but be not intended to limit its protection domain.Be that all equivalences of doing according to the content of the present patent application the scope of the claims change and modify, all should be technology category of the present invention.
Embodiment 1
Take hexanodioic acid (AR) and ethylene glycol (AR) is reaction system, and its mol ratio is 1: 1.2.By after raw material preheating to 160 degree Celsius, pass into continuously the tower staged reactor first step shown in Fig. 1, in every stage reactor, stop 25～35 minutes, guarantee that in each stage reactor, liquidus temperature progressively rises to 225 ℃ by 160 ℃ simultaneously.
Tower staged reactor last step outlet oligopolymer acid number is 35～45mgKOH/g, and hydroxyl value is 130～140mgKOH/g.
Embodiment 2
By passing into the tower staged reactor first step shown in Fig. 2 after oligopolymer mixing 25ppm isopropyl titanate in embodiment 1, in every stage reactor, stop 25～35 minutes, guarantee that in each stage reactor, liquidus temperature is 225 ℃ simultaneously.At different levelsly by tower top unification, vacuumized, guarantee that first step pressure is 2kPa (absolute pressure).
Tower staged reactor last step outlet polyester polyol product acid number is < 1mgKOH/g, and hydroxyl value is 70～80mgKOH/g, and water content < 0.02%.
Embodiment 3
Take hexanodioic acid (AR) and ethylene glycol (AR) is reaction system, and its mol ratio is 1: 1.2.By after raw material preheating to 160 degree Celsius, pass into continuously the tower staged reactor first step shown in Fig. 1, in every stage reactor, stop 25～35 minutes, guarantee that in each stage reactor, liquidus temperature progressively rises to 225 ℃ by 160 ℃ simultaneously.
Tower staged reactor last step outlet oligopolymer acid number is 35～45mgKOH/g, and hydroxyl value is 130～140mgKOH/g.
Embodiment 4
By passing into the tower staged reactor first step shown in Fig. 2 after oligopolymer mixing 25ppm isopropyl titanate in embodiment 3, in every stage reactor, stop 25～35 minutes, guarantee that in each stage reactor, liquidus temperature is 225 ℃ simultaneously.At the bottom of tower, pass into a large amount of high pure nitrogens, guarantee that the dividing potential drop of water and ethylene glycol remains on lower than them the equilibrium pressure in melt.
Tower staged reactor last step outlet polyester polyol product acid number is < 1mgKOH/g, and hydroxyl value is 70～80mgKOH/g, and water content < 0.02%.
Embodiment 5
Take hexanodioic acid (AR) and ethylene glycol (AR) is reaction system, and its mol ratio is 1: 1.15.By after raw material preheating to 160 degree Celsius, pass into continuously the tower staged reactor first step shown in Fig. 1, in every stage reactor, stop 30～40 minutes, guarantee that in each stage reactor, liquidus temperature progressively rises to 225 ℃ by 160 ℃ simultaneously.
Tower staged reactor last step outlet oligopolymer acid number is 35～45mgKOH/g, and hydroxyl value is 120～130mgKOH/g.
Embodiment 6
By passing into the tower staged reactor first step shown in Fig. 2 after oligopolymer mixing 25ppm isopropyl titanate in embodiment 5, in every stage reactor, stop 30～40 minutes, guarantee that in each stage reactor, liquidus temperature is 225 ℃ simultaneously.At different levelsly by tower top unification, vacuumized, guarantee that first step pressure is 2kPa (absolute pressure).
Staged reactor last step outlet polyester polyol product acid number is < 1mgKOH/g, and hydroxyl value is 50～60mgKOH/g, and water content < 0.02%.
Embodiment 7
Take hexanodioic acid (AR) and ethylene glycol (AR) is reaction system, and its mol ratio is 1: 1.15.By after raw material preheating to 160 degree Celsius, pass into continuously the tower staged reactor first step shown in Fig. 1, in every stage reactor, stop 30～40 minutes, guarantee that in each stage reactor, liquidus temperature progressively rises to 225 ℃ by 160 ℃ simultaneously.
Tower staged reactor last step outlet oligopolymer acid number is 35～45mgKOH/g, and hydroxyl value is 120～130mgKOH/g.
Embodiment 8
By passing into the tower staged reactor first step shown in Fig. 2 after oligopolymer mixing 25ppm isopropyl titanate in embodiment 7, in every stage reactor, stop 30～40 minutes, guarantee that in each stage reactor, liquidus temperature is 225 ℃ simultaneously.At the bottom of tower, pass into a large amount of high pure nitrogens, guarantee that the dividing potential drop of water and ethylene glycol remains on lower than them the equilibrium pressure in melt.
Tower staged reactor last step outlet polyester polyol product acid number is < 1mgKOH/g, and hydroxyl value is 50～60mgKOH/g, and water content < 0.02%.
Embodiment 9
Take hexanodioic acid (AR) and butyleneglycol (AR) is reaction system, and its mol ratio is 1: 1.2.By after raw material preheating to 160 degree Celsius, pass into continuously the tower staged reactor first step shown in Fig. 1, in every stage reactor, stop 25～35 minutes, guarantee that in each stage reactor, liquidus temperature progressively rises to 225 ℃ by 160 ℃ simultaneously.
Tower staged reactor last step outlet oligopolymer acid number is 35～45mgKOH/g, and hydroxyl value is 130～140mgKOH/g.
Embodiment 10
By passing into the tower staged reactor first step shown in Fig. 2 after oligopolymer mixing 25ppm isopropyl titanate in embodiment 9, in every stage reactor, stop 25～35 minutes, guarantee that in each stage reactor, liquidus temperature is 225 ℃ simultaneously.At different levelsly by tower top unification, vacuumized, guarantee that first step pressure is 2kPa (absolute pressure).
Tower staged reactor last step outlet polyester polyol product acid number is < 1mgKOH/g, and hydroxyl value is 70～80mgKOH/g, and water content < 0.02%.
Embodiment 11
Take hexanodioic acid (AR), phthalic anhydride (AR) and butyleneglycol (AR) is reaction system, and its mol ratio is 0.5: 0.5: 1.2.By after raw material preheating to 160 degree Celsius, pass into continuously the tower staged reactor first step shown in Fig. 1, in every stage reactor, stop 30～40 minutes, guarantee that in each stage reactor, liquidus temperature progressively rises to 225 ℃ by 160 ℃ simultaneously.
Tower staged reactor last step outlet oligopolymer acid number is 35～45mgKOH/g, and hydroxyl value is 130～140mgKOH/g.
Embodiment 12
By passing into the tower staged reactor first step shown in Fig. 2 after oligopolymer mixing 50ppm isopropyl titanate in embodiment 11, in every stage reactor, stop 30～40 minutes, guarantee that in each stage reactor, liquidus temperature is 225 ℃ simultaneously.At different levelsly by tower top unification, vacuumized, guarantee that first step pressure is 2kPa (absolute pressure).
Tower staged reactor last step outlet polyester polyol product acid number is < 1mgKOH/g, and hydroxyl value is 70～80mgKOH/g, and water content < 0.02%.
Claims (7)
1. a Multistage tower-type reactor is in the application of continuous production of polyesters polyvalent alcohol, this reactor is mainly formed with tower core is nested by Wai Ta, outer tower forms at the bottom of being provided with tower top, the tower body of material inlet and volatiles outlet and being provided with the tower of material outlet, Heat preservation chuck (7) is installed at the bottom of tower body and tower, tower core is nested in outer tower, tower core is multistage overflow bubble tower, is applied to the esterification of polyester polyol quantity-produced and/or transesterify stage and polycondensation phase; Reaction raw materials (1) is through being preheated to 90～260 ℃, be continuously fed into first step overflow bubble tower, material completes step by step from top to bottom reaction under 130～260 ℃ and 0.1～2 kilogram of pressure in tower reactor, by higher level's overflow bubble tower (10) overflow, through downtake (11), flow to next stage overflow bubble tower, until at the bottom of outflow reactor tower, obtain reaction product (14); At the bottom of rare gas element (13) is introduced to reactor column by sparger (12), from bottom to top converge step by step, from reactor head, with other small molecules, discharge system, it is on the one hand as shielding gas, suppress polymer degradation, also reduce on the other hand small molecules dividing potential drop, contribute to small molecules to remove, pass into the rare gas element of system before contacting with polymkeric substance, be preheating to polymer temperature or higher than polymer temperature; The small molecules steam that in overflow bubble towers at different levels, reaction produces and the polyvalent alcohol of vaporization, by bubbling tracheae bubbling, from bottom to top converge step by step and tower top, for esterification and/or transesterify elementary reaction, overhead vapor is through (2) separation of packing tower joint, most of alcohol returns to first step overflow bubble tower with phegma, most of water and other small molecules distillates (3) are discharged from tower top, after interchanger (4) is cooling, part is returned to packing tower joint (2) as phegma (6), and rest part is as waste liquid (5) discharge system; For polycondensation phase reaction, overhead vapor is directly as distillate (3) discharge system, and condensable gases is used as reclaiming alcohol after condensation; Overflow bubble towers at different levels (10) aspect ratio is 0.2～2, bubbling tracheae (8) connects suitable gas distributor simultaneously, to guarantee necessary bubbling effect and suitable plate pressure drop, the residence time of overflow bubble tower materials at different levels is 5～50 minutes, the relatively long residence time, to guarantee fully carrying out of reaction.
2. application as claimed in claim 1, it is characterized in that, be applied to the esterification of polyester polyol quantity-produced and/or transesterify stage and polycondensation phase, for esterification and/or transesterify stage: reaction raw materials is at least one or multiple polycarboxylic acid and/or polycarboxylic acid derivative and at least one or multiple polyvalent alcohol and/or polyol derivative
(a) polycarboxylic acid and derivative thereof comprise the organic polycarboxylic acid that has certain carbon atom and have 2～4 carboxyls, and derivative, suitable polycarboxylic acid and derivative thereof comprise: acid anhydrides and the derivative thereof of aliphatics polycarboxylic acid, alicyclic polycarboxylic acid, unsaturated alkyl polycarboxylic acid, aromatic polycarboxylic acid and aforementioned polycarboxylic acid, and aliphatics polycarboxylic acid comprises: succinic acid, pentanedioic acid, hexanodioic acid, pimelic acid, suberic acid, nonane diacid, sebacic acid, undecane diacid, dodecanedioic acid; Alicyclic polycarboxylic acid comprises: hexahydrobenzene dioctyl phthalate, 1,3-cyclohexane diacid, Isosorbide-5-Nitrae-cyclohexane diacid; Unsaturated alkyl polycarboxylic acid comprises: FUMARIC ACID TECH GRADE, maleic acid; Aromatic polycarboxylic acid comprises: phthalic acid, m-phthalic acid, terephthalic acid, 1,2,4-benzene tricarboxylic acid, 1,3,5-benzene tricarboxylic acid, NDA; The acid anhydrides of polycarboxylic acid comprises: maleic anhydride, Tetra hydro Phthalic anhydride, TMA,
(b) polyvalent alcohol and derivative thereof comprise the organic polyhydric alcohol that has certain carbon atom and have 2～4 hydroxyls, and derivative, suitable polyvalent alcohol and derivative thereof comprise: dibasic alcohol, trivalent alcohol, tetravalent alcohol and derivative thereof, dibasic alcohol comprises: ethylene glycol, glycol ether, polyoxyethylene glycol, 1,2-propylene glycol, 1, ammediol, dipropylene glycol, 1,4-butyleneglycol, neopentyl glycol, 1,6-hexylene glycol, 1,10-decanediol, 1,3-cyclohexanedimethanol, 1,4 cyclohexane dimethanol; Trivalent alcohol comprises: glycerine, TriMethylolPropane(TMP); Tetravalent alcohol comprises: tetramethylolmethane,
(c) polycarboxylic acid and derivative thereof and polyvalent alcohol and derivatives reaction mol ratio thereof are 1: 1～1: 4,
Polycondensation phase: reaction raw materials is the polyester polyol low-molecular-weight oligomer that at least one or multiple polycarboxylic acid and/or polycarboxylic acid derivative and at least one or multiple polyvalent alcohol and/or polyol derivative generate, catalyzer is at least one or multiple titanium system, antimony system, germanium system, tin system and tungsten series catalysts and composition thereof
(a) catalyzer is selected from following compounds: one or more in isopropyl titanate, tetrabutyl titanate, titanium ethylene glycolate, antimonous oxide, antimony acetate, antimony glycol, germanium dioxide, dibutyl tin laurate, phospho-wolframic acid,
(b) catalyzer usage quantity is 10～1000ppm of raw material total mass.
3. application as claimed in claim 2, is characterized in that polycondensation phase catalyzer (a) is selected from resistant to hydrolysis titanium catalyst.
4. application as claimed in claim 1 or 2, it is characterized in that, reaction raw materials (1) is through being preheated to 90～260 ℃, be continuously fed into first step overflow bubble tower, material completes step by step from top to bottom reaction under 130～260 ℃ and 0.1～2 kilogram of pressure in tower reactor, by higher level's overflow bubble tower (10) overflow, through downtake (11), flow to next stage overflow bubble tower, until at the bottom of outflow reactor tower, obtain reaction product (14); The small molecules steam that in overflow bubble towers at different levels, reaction produces and the polyvalent alcohol of vaporization, by bubbling tracheae (8) bubbling from bottom to top, with the liquid material countercurrent flow flowing downward, converge step by step and tower top, without or through (2) separation of packing tower joint, obtain overhead product (3).
5. application as claimed in claim 1, is characterized in that, at the bottom of reactor column, by sparger (16), introduces quite and raw material 0.1～10%wt polyvalent alcohol (15), further reduces the acid number of (14).
6. application as claimed in claim 1, is characterized in that, in overflow bubble towers at different levels (10), all has heating coil heat supply, guarantees that reaction mass is at 130～260 ℃.
7. application as claimed in claim 1, is characterized in that, the size of overflow ducts in overflow bubble towers at different levels, and bubbling tracheae size, quantity and the gas distributor form connecting thereof, size all need change and change with progression.
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| KR20190076681A (en) * | 2017-12-22 | 2019-07-02 | 서울대학교산학협력단 | Method for Preparing Polyalkylene Terephthalate glycol |
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