CN102040468A - Process for recycling feedstock from polyester wastes and apparatus using the same - Google Patents
Process for recycling feedstock from polyester wastes and apparatus using the same Download PDFInfo
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- CN102040468A CN102040468A CN2010100033280A CN201010003328A CN102040468A CN 102040468 A CN102040468 A CN 102040468A CN 2010100033280 A CN2010100033280 A CN 2010100033280A CN 201010003328 A CN201010003328 A CN 201010003328A CN 102040468 A CN102040468 A CN 102040468A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
- C08J11/10—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation
- C08J11/18—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material
- C08J11/22—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds
- C08J11/24—Recovery or working-up of waste materials of polymers by chemically breaking down the molecular chains of polymers or breaking of crosslinks, e.g. devulcanisation by treatment with organic material by treatment with organic oxygen-containing compounds containing hydroxyl groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
- C07C29/76—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment
- C07C29/80—Separation; Purification; Use of additives, e.g. for stabilisation by physical treatment by distillation
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/03—Preparation of carboxylic acid esters by reacting an ester group with a hydroxy group
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W30/00—Technologies for solid waste management
- Y02W30/50—Reuse, recycling or recovery technologies
- Y02W30/62—Plastics recycling; Rubber recycling
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- Polymers & Plastics (AREA)
- Crystallography & Structural Chemistry (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention relates to a process for recycling feedstock from polyester wastes and an apparatus using the same, and more particularly, to a process for recycling dimethyl terephthalate and ethylene glycol or feedstock for polyester from polyethyleneterephthalate (PET) and an apparatus using the same. More particularly, the present invention relates to a novel continuous recycling process for improving a process efficiency and energy saving effect through recycling of produced methanol vapor and crystallization of dimethyl terephthalate.
Description
Technical field
The present invention relates to by the method for polyester waste material recirculation raw material and the device that utilizes described method, more particularly, the present invention relates to by the polyester waste material that mainly comprises polyethylene terephthalate (hereinafter referred to as PET) (bottle, magnetic film, Beer Bottle, oligopolymer slag etc.) recirculation dimethyl terephthalate (DMT) (hereinafter referred to as DMT) and ethylene glycol (hereinafter referred to as EG) or polyester with the method for raw material and the device that utilizes described method.
Background technology
Now, owing to the development of plastics industry makes plastics spread unchecked, so waste material be treated as serious environmental problem.
Landfill, burning and recirculation are mainly adopted in the processing of plastic waste, preferably plastic waste are carried out recirculation, and this is because landfill and burning cause problems such as for example environmental pollution.Usually, recirculation can be divided into material recirculation and chemical re-circulation.In material recirculation, at first the plastic waste that generates is collected and classified, carry out physics recirculation then.Yet although the recirculation cost of material recirculation is comparatively economical, its problem is the plastics low quality of recirculation.
During chemical re-circulation,, obtained the monomer or the polymer raw of plastics with the plastic waste depolymerization.In an example, the pet waste of plastic waste has been carried out recirculation, traditional technology comprises following process:
Separating collecting process is enclosed in the ethylene glycol that contains the depolymerization catalyzer in the glycolysis reactor polyester waste material with the polyester waste material depolymerization to be two hydroxy esters (BHET) of terephthalic acid and oligopolymer, in the transesterification reactor of then product of part glycolysis being packed into, in the presence of transesterification catalyst, make thick DMT and EG by the transesterify of part glycolysis product in methyl alcohol (MeOH), and, simultaneously methyl alcohol is recycled in the transesterification reactor by utilizing distillation and crystallisation process to come thick DMT of purifying and EG to obtain final product DMT and EG thus.
About the transesterification reactor in the aforementioned process, United States Patent (USP) the 5th, 051, disclose for No. 528 and made superheated methanol gas oligopolymer or the dimethyl terephthalate (DMT) by ethylene glycol and terephthalic acid under low pressure, gasiform DMT, EG and methyl alcohol can be handled more contaminated PET thus by recovered overhead.That is to say, obtain BHET and oligopolymer, by the methyl alcohol alcoholysis effect acquisition DMT and the EG of BHET and oligopolymer by the part glycolysis.But, be that BHET will spend the very long reaction times by the depolymerization of part glycolysis, reason is that this is reversible reaction.
In addition, BHET that obtains and oligopolymer are by gaseous methanol depolymerization and form DMT and the EG that discharges with the gas phase form once more.Therefore, can not use high pressure methyl alcohol, speed of response thereby slow.
Disclosed the whole bag of tricks that is used for the alcoholysis of PET methyl alcohol in the patent documentation.Operate under the batch conditions and the condition of continuity and carry out, the subject matter of successive processes is to be difficult to the solid polyester waste material is supplied in the methyl alcohol alcoholysis reaction device of operation under high pressure.Because due to the previous reasons, although there are various disadvantages in intermittent process, the methyl alcohol alcoholysis is often carried out with intermittent process.The high pressure intermittent process is well-known to be: because the concentration of methyl alcohol keeps the higher level thereby the depolymerization of polyester to carry out fast in the oligomer solution, but because the concentration augmenting response speed of DMT that generates and EG reduces in time because of the restriction of molecular balance, therefore polyester fully depolymerization be DMT and EG, still have about 15% form that is left oligopolymer.
On the contrary, because DMT and EG remove by the top of reactor, so low pressure continuous solution collecting process is not subjected to the restriction of molecular balance, but its disadvantage is that speed of response is slower, and this is because the concentration of methyl alcohol remains on due to the lower level in the reaction soln.
Korean Patent be for No. 0837781 the applicant in first to file, it discloses following method: glycolysis reaction and methyl alcohol alcoholysis reaction are carried out in single reaction vessel simultaneously, unique high-pressure reactor thereby be used as polyester dissolving tank, glycolysis reactor and methyl alcohol alcoholysis reaction device.Preceding method can enlarge markedly speed of response, and obtains to reduce the effect of the consumption of material benzenemethanol because of the increase of reaction efficiency.
But, be wherein to carry out in the methyl alcohol alcoholysis reaction device and Methanol Recovery process of subsequent process, to need complex appts inevitably and consume big energy, liquefaction is from the methanol steam of methyl alcohol alcoholysis reaction device, make the methyl alcohol evaporating course by the high-pressure pump injection of methanol or from the raw material of methyl alcohol reservoir and by vaporizer.
Therefore, the disadvantage of aforementioned process need to be complicated apparatus and to consume relative lot of energy, reason is that liquefaction and evaporation repeat along with the methyl alcohol of collecting in the methanol distillation column evaporates by vaporizer in the methyl alcohol reservoir to be transported in the methyl alcohol alcoholysis reaction device to be stored in then once more through liquefaction.
Summary of the invention
Technical problem
Embodiments of the present invention aim to provide by the method such as polyester waste material recirculation raw materials such as bottle, magnetic film, oligopolymer slags, but described method simplification device, save energy and obtain highly purified monomer DMT.
More specifically, at first, embodiments of the present invention aim to provide a kind of method, wherein in rectifying tower (300) by the product separation of methanol that promptly makes in second reactor (200) at methyl alcohol alcoholysis reaction device, and make it be recycled to second reactor (200), and need not condensation or evaporation once more, significantly save the big energy that the methyl alcohol because of the repeated evaporation and the recirculation of liquefying consumes thus and simplified device.
Secondly, another embodiment of the invention aims to provide a kind of method, it directly contacts with the liquid cell (for example by immersing) of rectifying tower (300) bottom by making the gaseous reaction products of discharging through the top of second reactor (200), and directly contact with liquid the column plate of the rectifying tower that flows down from methyl alcohol reservoir (30) or the post part (column section), thereby direct liquefaction DMT and EG and the methyl alcohol in the evaporating solns only can make highly purified methyl alcohol be recycled to second reactor (200) thus and use this methyl alcohol in the methyl alcohol alcoholysis reaction.
The 3rd, another embodiment of the present invention aims to provide a kind of method, the feeding amount of adjusting methyl alcohol when it can be recycled to second reactor (200) when mixing the isolated methyl alcohol of gaseous reaction products institute of being discharged by the top of second reactor (200) with the material benzenemethanol of being supplied by methyl alcohol reservoir (30) and with this mixture.
The 4th, another embodiment of the present invention aims to provide a kind of method, wherein deliver to the methyl alcohol of second reactor (200) and supplied with by the isolating methyl alcohol of rectifying tower (300), need not to retain methanol evaporator, well heater and high-pressure pump thus, rectifying tower has been brought into play their effect.
The 5th, another embodiment of the present invention aims to provide a kind of method, and it only evaporates methyl alcohol by the temperature of control rectifying tower (300) bottom, helps follow-up crystallization thus.The 6th, another embodiment of the present invention aims to provide a kind of method, it is conditioned reaction condition and rectifying condition freely, thereby when the amount of the methyl alcohol of discharging through the top of rectifying tower (300) is too much, use back pressure type setter (31) that a part of methyl alcohol is stored in the methyl alcohol reservoir, improve productivity thus.
Technical scheme
Advantage of the present invention, feature and each scheme will be become apparent by the description of the following embodiment with reference to the accompanying drawings of illustrating hereinafter.
Unless limit in addition, herein the implication and common understand identical of those skilled in the art that have of the scientific and technical term of all of Shi Yonging.In other situation, well-known function and structure are not done detailed description, and the present invention is unnecessarily fuzzy to be difficult to resolve to avoid making.
Fig. 1 is the synoptic diagram of demonstration by the whole process of the device of polyester waste material recirculation raw material DMT and EG, the inventive system comprises raw material feeder (10); First reactor (100), described first reactor (100) use the described raw material by described raw material feeder (10) supply to carry out glycolysis reaction and methyl alcohol alcoholysis reaction in single reaction vessel; Second reactor (200), described second reactor (200) are used for the product of described first reactor (100) is carried out the methyl alcohol alcoholysis reaction; Rectifying tower (300), described rectifying tower (300) are used for from through the top of described second reactor (200) expellant gas separation of methanol and make isolating gaseous methanol be recycled to described second reactor (200); With methyl alcohol reservoir (30), described methyl alcohol reservoir (30) is used for methyl alcohol is provided to described rectifying tower (300).
To be described in detail each parts.
Raw material feeder of the present invention (10) is the raw material supply device, can adopt forcing machine, screw feeder or air lock valve, but be not limited to this.
First reactor of the present invention (100) is glycolysis/methyl alcohol alcoholysis reaction device that glycolysis reaction and methyl alcohol alcoholysis reaction wherein take place simultaneously, it need not independent dissolving tank, because DMT and oligopolymer just generate therein, and can enlarge markedly depolymerization speed.
Second reactor (200) makes and carries out the methyl alcohol alcoholysis reaction from the reactant of first reactor (100) transmission with the methyl alcohol of being supplied by the bubble generator (90) of second reactor lower part, and when finishing depolymerization, discharge gaseous reaction products, can handle the rudimentary polyester waste material that comprises many impurity thus.
In addition, rectifying tower (300) makes the liquid cell of the direct contact rectification tower of the product of second reactor (200) (300) bottom and the column plate of the rectifying tower that flows down from methyl alcohol reservoir (30) or the liquid the post part, thereby, and make the isolating methyl alcohol and the mixture of the material benzenemethanol of supplying by methyl alcohol reservoir (30) be recycled to the top of rectifying tower (300) and be evaporated to second reactor (200) with methyl alcohol evaporation and separation separately.
In addition, be used for when the operation beginning, also supplying methyl alcohol to first reactor (100) to the methyl alcohol reservoir (30) of rectifying tower (300) supply methyl alcohol.
Device by polyester waste material recirculation raw material of the present invention can also comprise back pressure type setter (31), it is used to control the pressure of rectifier and methyl alcohol alcoholysis reaction device (200), from the steam methanol condensed of back pressure type setter and be stored in the methyl alcohol reservoir (30); Crystallizer tank (400), it is used for making the liquid crystallization of DMT from rectifying tower (300); Solid-liquid separator (500), it is used for the DMT of fractional crystallization; Distillation tower (600), its be used at an upper portion thereof from the liquid methanol that is rich in EG isolate methyl alcohol with isolating methyl alcohol be stored in the methyl alcohol reservoir (30) and from the liquid methanol that is rich in EG, isolate oligopolymer so that the isolating oligopolymer of institute is recycled in first reactor (100) in its underpart.
In addition, device of the present invention also can comprise storage in the waste material between raw material feeder (10) and first reactor (100), its be used to weigh by the raw material of raw material feeder supply and with the raw material supply of weighing to reactor.
In addition, the transfer tube (70a) that is used to transfer to second reactor (200) also dispose the transmitter that is used to detect the liquid level in second reactor (200) and the liquid-level controller that utilizes described sensor detecting liquid level and regulate liquid level with automatic open valve (80a) when liquid level reduces.
Can use back pressure type setter (31) or other pressure regulator valves to regulate second pressure that reacts in (200) and the rectifying tower (300) by controlling the effusive part methyl alcohol in rectifying tower top.
In addition, preferably also dispose the condenser that is used for condensation methyl alcohol, thereby when the amount of the methyl alcohol of discharging via the top of rectifying tower (30) is too much, part methyl alcohol is collected into methyl alcohol reservoir (30) on the top of methyl alcohol reservoir (30).
Then, the invention provides a kind of method, it is by part glycolysis reaction and methyl alcohol alcoholysis reaction and purifying and from the raw material of polyester such as PET recirculation DMT and EG.
Particularly, method by polyester raw materials such as polyester waste material recirculation DMT and EG according to the present invention comprises: pack in first reactor (100) with raw material with from the EG of the predetermined amount of distillation tower (600) or oligopolymer and depolymerization mixture of catalysts, thereby and make described raw material depolymerization by the pressure in the methyl alcohol augmenting response device without interruption; The transmission valve (80a) of opening the transfer tube (70a) that is connected with second reactor (200) when depolymerization is finished is with the reactant of transmission from first reactor (100); The gaseous reaction products that generates in second reactor (200) is transferred to rectifying tower (300), and remaining methyl alcohol, DMT and EG liquefy from pure methyl alcohol and in the bottom of described tower on the top of described tower; To be recycled to second reactor (200) and the part of described methyl alcohol will be stored in the methyl alcohol reservoir (30) at the isolating methyl alcohol in the top of rectifying tower (300); To transfer to crystallizer tank (400) so that the DMT crystallization from the effusive liquid in bottom of rectifying tower (300); To transfer to solid-liquid separator (500) from the product of crystallizer tank (400) to separate DMT crystal and the liquid methanol that is rich in EG; The liquid methanol that is rich in EG is transferred to distillation tower (600) with separation EG, oligopolymer and methyl alcohol, and described methyl alcohol is stored in the methyl alcohol reservoir (30), oligopolymer is recycled to described first reactor (100).
First reactor (100) is connected by transfer tube (70a) with second reactor (200), thereby described reactant transmits by pressure reduction.More specifically, when the liquid level in second reactor (200) reduced, the transmission valve (80a) of transfer tube (70a) was opened automatically, and reactant transfers to second reactor (200) by pressure reduction by first reactor (100).
In addition, first reactor (100) moves in 200 ℃～300 ℃ temperature and normal atmosphere to the reaction pressure of 50bar, second reactor (200) moves to the reaction pressure of 10bar in 200 ℃～300 ℃ temperature and normal atmosphere, and reactant can transmit automatically thus.
In addition, can be with isolating EG in the distillation tower (600) as the raw material in first reactor (100) of can packing into.
More specifically, used raw material is a polyester waste material in the method for the present invention, and by sending into first reactor (100) such as raw material feeders (10) such as forcing machine, screw feeder and air lock valves.Polyester waste material can be with powder with suitable size to solid form feeds such as thin slices, perhaps with fusion form feed.First reactor (100) can be with the operation of continuous, semicontinuous or batch type, reacts BHET, MHET or the oligopolymer that can depolymerization obviously reduces as molecular weight through glycolysis by using polyester that reactor has a macromolecule.
In addition, carry out, therefore generate quite a large amount of DMT in first reactor (100) because methyl alcohol alcoholysis reaction and glycolysis reaction walk abreast.In this process, because the EG that generates by the methyl alcohol alcoholysis can be used for glycolysis once more, therefore two reaction and display go out collaborative mutually.In addition, the EG of generation itself can be used to dissolve the PET raw material of new supply, so the feeding amount of the required EG of glycolysis can obviously reduce, or need not to send into EG.
When the EG that will comprise catalyzer and oligopolymer sends in first reactor (100), thereby polyester waste material takes place to consume significantly in glycolysis reaction and methyl alcohol alcoholysis reaction simultaneously, thereby transforms into DMT and this process subsequently of EG is easy to quick generation in second reactor (200).By regulating the pressure that the amount of sending into the methyl alcohol in first reactor (100) through transfer tube (120b) by methyl alcohol reservoir (30) can be regulated first reactor (100).
First reactor (100) is connected by transfer tube (70a) with second reactor (200), thereby reactant transmits by pressure reduction.More specifically, when the liquid level in second reactor (200) reduced, the transmission valve (80a) of transfer tube (70a) was opened automatically, and reactant transfers to second reactor (200) by pressure reduction by first reactor (100).
For second reactor of the present invention (200), methyl alcohol is delivered to the bottom of reactor by bubble generator (90).When the methyl alcohol of delivering to described bottom and the reactant that is transmitted by first reactor (100) are in direct contact with one another the methyl alcohol alcoholysis reaction taking place, discharges gaseous reaction products through the top of second reactor (200) thus.In this process, the function of methyl alcohol is not only reaction material, but also is used as carrier so that reaction product is discharged together with methanol vapor self.
The reaction product that makes in second reactor (200) when the transmission valve (80b) of transfer tube (70b) is opened transfers to rectifying tower (300), and and liquid, promptly the solution of DMT, EG and methyl alcohol contacts in the bottom of rectifying tower (300).Therefore, only make methyl alcohol separated at the top of tower, and methyl alcohol, DMT and EG liquefy in the bottom of tower, this makes crystallisation process subsequently more favourable.Along with the liquid that flows downward when the methyl alcohol of supplying raw materials refluxes and the mobile gaseous methanol that makes progress are in contact with one another in column plate or filler, the separation of methyl alcohol is accomplished.Adopt said process can improve the separation efficiency of methyl alcohol and other products.
Methanol vapor is in the recovered overhead of rectifying tower (300), and most of compressed machine of methanol vapor (61) or gas blower that reclaims is recycled to the continuous methyl alcohol alcoholysis reaction of low pressure device, promptly in second reactor (200).
Use back pressure type setter (31) or other pressure regulator valves can regulate pressure in second reactor (200) and the rectifying tower (300) by regulating in the outflow of the part methanol vapor of rectifying tower (300) recovered overhead.In addition, when the amount of the methyl alcohol of being discharged by the top of rectifying tower (300) was too much, the part methanol vapor can flow out by back pressure type setter (31), and condensation is stored in the methyl alcohol reservoir (30).
Therefore, the present invention has saved lot of energy than existing method, and existing method evaporation is delivered in the depolymerizing reactor by the material benzenemethanol of methyl alcohol reservoir (30) supply and with the methyl alcohol of evaporation.In addition, along with the recovery of methyl alcohol in rectifying tower (300) top, DMT and EG concentrate in the bottom of rectifying tower (300), and this helps crystallisation process subsequently.
Transfer to crystallizer tank (400) by effusive DMT of rectifying tower (300) and EG and carry out crystallisation process.DMT moves to solid-liquid separator (500) then by concentrating or crystallisation by cooling.In solid-liquid separator, use whizzer or strainer to separate DMT crystal and the liquid methanol that is rich in EG.The advantage of the DMT that obtains by said process is that the organic efficiency of DMT is quite high, and can obtain very high purity.
The liquid methanol that is rich in EG is the liquid that contains excessive EG and methyl alcohol, and it also comprises a spot of oligopolymer.
Subsequently, the liquid methanol that is rich in EG transfers to distillation tower (600) and carries out follow-up sepn process to be separated into EG, oligopolymer and methyl alcohol.At this moment, distillation tower (600) can be with continous way or periodic running.Isolating methyl alcohol is stored in the methyl alcohol reservoir (30) in the distillation tower (600), and oligopolymer can be recycled to first reactor (100) via transfer tube (130), and EG is stored in the EG reservoir.
Advantageous effects
According to the present invention, by the methyl alcohol alcoholysis product from methyl alcohol alcoholysis reaction device (200) is directly contacted with liquefaction DMT and EG with the liquid cell of tower bottom, and evaporation is from the material benzenemethanol as reflux in the rectifying tower (300) of methyl alcohol reservoir, thereby can separate gaseous methanol in rectifying tower (300).In addition, because isolating gaseous methanol is recycled to second reactor (200) via recycle compressor (61) or gas blower in the rectifying tower, and the bubble generator (90) by second reactor (200) bottom directly contacts with generation methyl alcohol alcoholysis reaction with polyester liquid in the inside of reactor, can save the energy cost because of repeating to evaporate and liquefy and produced in the existing methyl alcohol process recycling significantly.In addition, because needn't use existing used methanol evaporator, well heater and the high-pressure pump of methyl alcohol process recycling, can simplification device and remarkable economy system cost.
In addition, regulate pressure in second reactor (200) and the rectifying tower (300) by controlling by the top effluent air of rectifying tower (300), freely conditioned reaction condition and rectifying condition, and can also obtain monomeric high organic efficiency and highly purified monomer DMT by introducing crystallizer tank (400) and solid-liquid separator (500).
Description of drawings
Fig. 1 is the schematic representation of apparatus that shows by polyester waste material recirculation raw material.
The detailed description of major parts
10: the raw material feeder
30: the methyl alcohol reservoir
31: the back pressure type setter
61: recycle compressor
90: bubble generator
100: the first reactors
200: the second reactors
300: rectifying tower
400: crystallizer tank
500: solid-liquid separator
600: distillation tower
70a, 70b, 110a, 120a, 120b, 130: transfer tube
80a, 80b: transmission valve
Embodiment
To describe apparatus and method below in detail by polyester waste material recirculation raw material.
At first, raw materials such as polyester waste material are put into raw material feeder (10), send into first reactor (100) then.Raw material feeder (10) is the raw material supply device, can adopt forcing machine, screw feeder or air lock valve, but be not limited to this.Polyester waste material can be with powder with suitable size to solid form feeds such as thin slices, perhaps with fusion form feed.First reactor (100) can move with types such as continuous, semicontinuous or intermittences.The EG and the methyl alcohol of predetermined amount are injected first reactor (100) with the generation depolymerization reaction, and isolating oligopolymer in the distillation tower (600) can be put into first reactor (100) where necessary to participate in reaction.With the temperature of reactor rise to temperature required after, material benzenemethanol is supplied to first reactor (100) by methyl alcohol reservoir (30) through transfer tube (120b), so that the pressure in the reactor reaches required reaction pressure.At this moment, methyl alcohol is sent into continuously so that the pressure in the reactor is kept constant voltage.Because glycolysis reaction and methyl alcohol alcoholysis reaction under high pressure take place simultaneously in this first reactor (100), the molecular weight of polyester waste material significantly reduces, thereby polyester waste material becomes the solution state of DMT and oligopolymer.
In being in continuous second reactor (200) of low pressure, by first reactor (100) via the reactant of transfer tube (70a) and transmission valve (80a) transmission with from rectifying tower (300) through the methyl alcohol of bubble generator (90) supply in the reaction of the bottom of second reactor (200), so that the methyl alcohol alcoholysis reaction to take place.Reaction product is discharged with the gas phase form by the transfer tube (70b) and the transmission valve (80b) that are connected with reactor head.Therefore, the reactant of predetermined amount is transmitted by first reactor (100) when the liquid level in second reactor (200) reduces.At this moment, transmission is carried out automatically by pressure reduction.The bottom that preferably valve is arranged on transfer tube (70a) can be connected controller so that valve operation automatically by controller to control the liquid level of the inner reaction solution of second reactor (200) with the valve (80a) of transfer tube.
When first reactor (100) moves with intermittent mode, in first reactor (100) of transmission reactant to the second reactor (200), the solid polyester waste material of packing into, and send into oligopolymer and EG solution and methyl alcohol, can start new intermittent reaction by repeating said process like this.
That is to say that polyester waste material is converted into DMT and oligopolymer by reaction under high pressure in first reactor (100), discharge gaseous state DMT, EG, oligopolymer and methyl alcohol continuously by second reactor (200) by the methyl alcohol alcoholysis.At this moment, when the liquid level in second reactor (200) descended, the reactant in first reactor (100) transferred to second reactor (200) once more satisfying required liquid level, and in first reactor (100) the new intermittent process of beginning.
Simultaneously, the gaseous reaction products of being discharged by second reactor (200) is sent to rectifying tower (300) by transfer tube (70b), directly contacts to liquefy DMT and EG and evaporate methyl alcohol with the liquid cell of rectifying tower (300) bottom.Because methyl alcohol and other products by this direct contact separation, therefore can be saved big energy.
In addition, material benzenemethanol is injected the top of rectifying tower (300) so that it refluxes, the gas stream of this liquid flow and reaction product contacts with each other at column plate or packing section, with only make top portion that methyl alcohol passes through tower from.Use the recycle compressor (61) or the gas blower that are connected with rectifying tower (300) that isolating methanol vapor is injected second reactor (200).Afterwards, methyl alcohol contacts so that the methyl alcohol alcoholysis reaction to take place by the inner polyester liquid of bubble generator (90) and second reactor (200).
In addition, when the amount of the methyl alcohol of discharging via the top of rectifying tower (300) is too much, utilize back pressure type setter (31) or other pressure regulator valves that the part methanol gas is flowed out regulating the pressure in second reactor (200) and the rectifying tower (300), and after condensation, be stored in the methyl alcohol reservoir (30).
On the contrary, when the amount of the methyl alcohol of sending into second reactor (200) should increase, the methyl alcohol in the methyl alcohol reservoir (30) was sent into the top of rectifying tower (300) more and is evaporated to send into second reactor (200).Can regulate the concentration of the DMT of rectifying tower (300) bottom by the temperature of regulating the rectifying tower bottom.By regulate send into the injection rate (quantity of reflux) of the material benzenemethanol on rectifying tower (300) top through transfer tube (120a) by methyl alcohol reservoir (30) can controlled temperature, and when the recirculation flow velocity of considering methanol gas or circulation velocity, can determine the heat that adds of rectifying tower (300) bottom.
To transfer to crystallizer tank (400) with the methanol solution that is rich in EG at the DMT of rectifying tower (300) bottom liquefaction.DMT is crystallization by transpiration cooling, DMT and the liquid methanol that is rich in EG with the solid-liquid separator (500) of the adjacent layout of crystallizer tank (400) in separate.Subsequently, the liquid methanol that is rich in EG is transferred to distillation tower (600), and be separated into EG, methyl alcohol and some oligopolymer.Isolating methyl alcohol is stored in the methyl alcohol reservoir (30), and collects EG.In addition, the oligopolymer that distillation tower (600) bottom obtains is sent into first reactor (100), carry out depolymerization once more.
Although the present invention describes for embodiment, but what it will be apparent to those skilled in the art that is can carry out various changes and modifications and can not deviate from the spirit and scope of the present invention defined in claims.
Claims (16)
1. device by polyester waste material recirculation raw material, described device makes polyester with raw material dimethyl terephthalate (DMT) and ethylene glycol by polyester waste material, and described device comprises:
Raw material feeder (10);
First reactor (100), described first reactor (100) use the described raw material by described raw material feeder (10) supply to carry out glycolysis reaction and methyl alcohol alcoholysis reaction in single reaction vessel;
Second reactor (200), described second reactor (200) are used to make the product of described first reactor (100) to carry out the methyl alcohol alcoholysis reaction;
Rectifying tower (300), described rectifying tower (300) are used for from the top expellant gas separation of methanol by described second reactor (200) and make isolating gaseous methanol be recycled to described second reactor (200); With
Methyl alcohol reservoir (30), described methyl alcohol reservoir (30) are used for methyl alcohol is provided to described rectifying tower (300).
2. the product that device as claimed in claim 1, wherein said rectifying tower (300) make described second reactor (200) with described rectifying tower (300) thus the liquid cell of bottom directly contact and evaporates also separation of methanol separately.
3. device as claimed in claim 2, wherein said rectifying tower (300) will and provide the methanol mixture that need reflux and evaporate to the top of described rectifying tower (300) to be recycled to described second reactor (200) by described methyl alcohol reservoir (30) by isolating methyl alcohol in the product of described second reactor (200).
4. device as claimed in claim 2, described device comprise that also back pressure type setter (31) is to control the pressure of described methyl alcohol alcoholysis reaction device (200) and described rectifying tower (300).
5. as each described device in the claim 1～4, described device also comprises crystallizer tank (400), and described crystallizer tank (400) is used for making the liquid crystallization of dimethyl terephthalate (DMT) from described rectifying tower (300).
6. device as claimed in claim 5, described device also comprise solid-liquid separator (500), and described solid-liquid separator (500) is used to separate institute's crystalline dimethyl terephthalate (DMT).
7. device as claimed in claim 6, described device also comprises the distillation tower (600) that is connected with described solid-liquid separator (500), described distillation tower be used at an upper portion thereof from the liquid methanol that is rich in ethylene glycol isolate methyl alcohol with isolating methyl alcohol be stored in the described methyl alcohol reservoir (30) and from the liquid methanol that is rich in ethylene glycol, isolate oligopolymer so that the isolating oligopolymer of institute is recycled in described first reactor (100) in its underpart.
8. device as claimed in claim 1, described device also comprises storage in the waste material between described raw material feeder (10) and described first reactor (100), storage is used to weigh the raw material that provided by described raw material feeder and raw material supply that will be through weighing to described reactor in the described waste material.
9. device as claimed in claim 1, described device also comprises transmitter, described transmitter is used at the liquid level that detects in order to the transfer tube (70a) that transfers to described second reactor (200) in described second reactor (200).
10. device as claimed in claim 9, described device also are included in the valve (80a) that is connected with described transmitter in described second reactor (200), and described valve is opened when the liquid level by described sensor detecting reduces automatically.
11. device as claimed in claim 1, wherein said second reactor (200) comprises bubble generator (90), and described bubble generator (90) is used for the methyl alcohol through evaporation of supply from described rectifying tower (300).
12. the method by polyester waste material recirculation raw material, described method makes polyester raw material dimethyl terephthalate (DMT) and ethylene glycol by polyester waste material, and described method comprises:
The ethylene glycol of raw material and predetermined amount and depolymerization mixture of catalysts are packed in first reactor (100), thereby and the pressure that increases in the described reactor by methyl alcohol without interruption make described raw material depolymerization;
The transmission valve (80a) of opening the transfer tube (70a) that is connected with second reactor when depolymerization is finished is with the reactant of transmission from described first reactor (100);
The gaseous reaction products that generates in described second reactor (200) is transferred to rectifying tower (300), and remaining methyl alcohol, dimethyl terephthalate (DMT) and ethylene glycol liquefy from pure methyl alcohol and in the bottom of described tower on the top of described tower;
To be recycled to described second reactor (200) and the part of described methyl alcohol will be stored in the methyl alcohol reservoir (30) at the isolating methyl alcohol in the top of described rectifying tower (300);
To transfer to crystallizer tank (400) so that the dimethyl terephthalate (DMT) crystallization from the effusive liquid in bottom of described rectifying tower (300);
To transfer to solid-liquid separator (500) from the product of described crystallizer tank (400) with terephthalic acid isolated dimethyl ester crystal and the liquid methanol that is rich in ethylene glycol; With
The described liquid methanol that is rich in ethylene glycol is transferred to distillation tower (600) with separation ethylene glycol, oligopolymer and methyl alcohol, and described methyl alcohol is stored in the described methyl alcohol reservoir (30), described oligopolymer is recycled to described first reactor (100).
13. method as claimed in claim 12, wherein said first reactor (100) and described second reactor (200) through transfer tube (70a) thus be connected described reactant transmitted by pressure reduction.
14. method as claimed in claim 12, wherein said first reactor (100) moves to the reaction pressure of 50bar in 200 ℃～300 ℃ temperature and normal atmosphere, and described second reactor (200) moves in 200 ℃～300 ℃ temperature and normal atmosphere to the reaction pressure of 10bar.
15. method as claimed in claim 12, wherein when the liquid level in described second reactor (200) reduces, the transmission valve (80a) of described transfer tube (70a) is opened automatically, and described reactant transfers to described second reactor (200) by pressure reduction from described first reactor (100).
16. method as claimed in claim 12, wherein isolating ethylene glycol can be as the raw material in described first reactor (100) of packing in described distillation tower (600).
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR20090096032A KR101099009B1 (en) | 2009-10-09 | 2009-10-09 | Feedstock recycling process from polyester wastes and apparatus for using thereof |
| KR10-2009-0096032 | 2009-10-09 |
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| CN102040468A true CN102040468A (en) | 2011-05-04 |
| CN102040468B CN102040468B (en) | 2014-04-16 |
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| CN201010003328.0A Active CN102040468B (en) | 2009-10-09 | 2010-01-21 | Process for recycling feedstock from polyester wastes and apparatus using the same |
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| Country | Link |
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| JP (1) | JP5128618B2 (en) |
| KR (1) | KR101099009B1 (en) |
| CN (1) | CN102040468B (en) |
| WO (1) | WO2011043515A1 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219924A (en) * | 2011-06-01 | 2011-10-19 | 中国人民解放军总后勤部军需装备研究所 | Device for separating cotton-polyester blended fabrics and repolymerizing polyester |
| WO2021004070A1 (en) * | 2019-07-10 | 2021-01-14 | 艾凡佳德(上海)环保科技有限公司 | Recovery method for waste polyester material performed by means of continuous alcoholysis and continuous transesterification |
| CN117486720A (en) * | 2023-11-06 | 2024-02-02 | 浙江佳人新材料有限公司 | DMT remelting recovery process in chemical recycling process of waste textiles |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101347906B1 (en) | 2013-02-27 | 2014-01-08 | (주) 시온텍 | Feedstock recycling process from polyester wastes and apparatus for using thereof |
| KR101386683B1 (en) | 2013-02-27 | 2014-04-24 | (주) 시온텍 | Crystallizing process and its apparatus for chemical recycling waste polyester |
| KR101584059B1 (en) | 2014-03-10 | 2016-01-11 | (주)시온텍 | Feedstock recycling apparatus from polyester wastes |
| PL411679A1 (en) * | 2015-03-20 | 2016-09-26 | Rs Pet Spółka Z Ograniczoną Odpowiedzialnością | Installation for continuous processing of PET polyethylene terephthalate waste |
| CN111905395A (en) * | 2019-05-07 | 2020-11-10 | 上海浦景化工技术股份有限公司 | Rectification separation system and separation process for preparing ethylene glycol from synthesis gas |
| CN110527138B (en) * | 2019-07-10 | 2020-07-03 | 艾凡佳德(上海)环保科技有限公司 | Continuous alcoholysis recovery method of waste polyester |
| CN112295254B (en) * | 2020-11-09 | 2024-09-17 | 苏州市浒墅关化工添加剂有限公司 | High-efficient reaction equipment of rectification |
| LU102949B1 (en) | 2022-05-03 | 2023-11-06 | Univ Hamburg | Method for the depolymerization of a terephthalate polyester |
| EP4273190A1 (en) | 2022-05-03 | 2023-11-08 | Universität Hamburg | Method for the depolymerization of a terephthalate polyester |
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| US5712410A (en) * | 1997-03-03 | 1998-01-27 | Eastman Kodak Company | Gas phase crystallization of dimethyl terephthalate |
| JP3652895B2 (en) * | 1998-08-28 | 2005-05-25 | 三菱重工業株式会社 | Monomerization of polyethylene terephthalate |
| CN1203037C (en) * | 1999-10-22 | 2005-05-25 | 帝人株式会社 | Method for separating and recovering dimethyl terephthalate and ethylene glycol from polyester waste |
| JP2002114722A (en) * | 2000-10-06 | 2002-04-16 | Mitsubishi Heavy Ind Ltd | Reactional vessel and method for monomerizing polyester |
| JP2003300916A (en) | 2002-04-05 | 2003-10-21 | Mitsubishi Heavy Ind Ltd | Method for producing monomer from pet |
| JP2003300929A (en) * | 2002-04-05 | 2003-10-21 | Mitsubishi Heavy Ind Ltd | Method for producing monomer from pet |
| JP2004277638A (en) * | 2003-03-18 | 2004-10-07 | Teijin Fibers Ltd | Collecting method of highly pure terephthalic acid from polyester wastes |
| KR100837781B1 (en) * | 2007-04-17 | 2008-06-13 | 충남대학교산학협력단 | Feedstock recycling process from polyester wastes and apparatus for using thereof |
-
2009
- 2009-10-09 KR KR20090096032A patent/KR101099009B1/en active IP Right Grant
- 2009-12-22 WO PCT/KR2009/007667 patent/WO2011043515A1/en active Application Filing
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102219924A (en) * | 2011-06-01 | 2011-10-19 | 中国人民解放军总后勤部军需装备研究所 | Device for separating cotton-polyester blended fabrics and repolymerizing polyester |
| CN102219924B (en) * | 2011-06-01 | 2012-08-08 | 中国人民解放军总后勤部军需装备研究所 | Device for separating cotton-polyester blended fabrics and repolymerizing polyester |
| WO2021004070A1 (en) * | 2019-07-10 | 2021-01-14 | 艾凡佳德(上海)环保科技有限公司 | Recovery method for waste polyester material performed by means of continuous alcoholysis and continuous transesterification |
| CN117486720A (en) * | 2023-11-06 | 2024-02-02 | 浙江佳人新材料有限公司 | DMT remelting recovery process in chemical recycling process of waste textiles |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5128618B2 (en) | 2013-01-23 |
| KR20110038860A (en) | 2011-04-15 |
| WO2011043515A1 (en) | 2011-04-14 |
| CN102040468B (en) | 2014-04-16 |
| KR101099009B1 (en) | 2011-12-28 |
| JP2011079807A (en) | 2011-04-21 |
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