CN112409139B - Bisphenol A production method and device - Google Patents
Bisphenol A production method and device Download PDFInfo
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- C07C37/11—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom of a six-membered aromatic ring by reactions increasing the number of carbon atoms
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- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
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- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
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Abstract
The invention belongs to the technical field of bisphenol A production, and particularly relates to a bisphenol A production method and device. The bisphenol A production method comprises the following steps: step A: under the action of an acid catalyst, carrying out condensation reaction on excessive phenol and acetone to obtain a reaction solution containing bisphenol A; and (B) step (B): concentrating the reaction liquid to obtain a concentrated liquid; step C: the concentrated solution is further crystallized, and mother liquor I and an adduct filter cake of phenol and 4, 4-bisphenol A are obtained through solid-liquid separation; step D: the mother liquor I is subjected to isomerization treatment and separation to obtain mother liquor II and an adduct filter cake of phenol and 4, 4-bisphenol A; step E: and the mother solution II is used as a production raw material of the epoxy resin to react with an epoxy compound to generate the byproduct polyphenol epoxy resin. The production method can effectively reduce the impurity content in the device, reduce or even cancel the discharge of heavy residues, reduce the consumption of raw materials phenol and acetone, and improve the technical level of the device.
Description
Technical Field
The invention relates to the technical field of bisphenol A production, in particular to a bisphenol A production method and device.
Background
Bisphenol a is an important compound as a raw material for engineering plastics such as polycarbonate resins and polyarylate resins, and epoxy resins, and the demand for bisphenol a has been increasing in recent years. As a raw material for producing a high-quality resin, high-quality bisphenol a is required.
The CN104379546a discloses a process for producing bisphenol a (flow chart of which is shown in fig. 2), which comprises the following steps (a) to (F):
step (A): in the presence of an acid catalyst, generating BPA in a reactor for carrying out condensation reaction on excessive phenol and acetone to obtain a reaction mixed solution containing BPA;
step (B): dehydrating and concentrating the reaction mixed solution to obtain a dehydrated concentrated solution;
step (C): crystallizing the dehydrated concentrate, and then carrying out solid-liquid separation to obtain a solid component (adduct filter cake) and a mother liquor I;
step (D): isomerizing at least a portion of the mother liquor present in the system from among the mother liquor I;
step (E): concentrating, crystallizing and separating solid and liquid from the isomerized solution to obtain a phenol and 4, 4-bisphenol A adduct filter cake and a mother liquor II;
step (F): subjecting the mother liquor obtained in the step (E) to phenol recovery treatment, and decomposing bisphenol a, 2,4' -bisphenol a and triphenols present in the mother liquor by subjecting at least a part of the mother liquor present in the system to alkali decomposition treatment; recovering phenol and/or p-isopropenylphenol, synthesizing bisphenol A from the recovered phenol and/or p-isopropenylphenol by a rearrangement reaction, and supplying the bisphenol A to the reactor in the step (A).
However, in practical application, the method described in CN104379546a still has the defects of more impurities, larger discharge amount of heavy residues, high energy consumption in alkaline decomposition operation and the like; particularly, when heavy residues are discharged, the consumption of usable substances is increased, and the consumption of raw materials phenol and acetone is increased, so that the energy cost is increased.
The invention aims to provide a preparation method of bisphenol A, which can effectively reduce the content of impurities such as 2, 4-bisphenol A and the like in a device, greatly reduce the impurity amount returned to a reaction unit and reduce or even cancel heavy residue discharge. The method can remarkably reduce consumption of raw materials of phenol and acetone and improve the technical level of the device.
Disclosure of Invention
In order to solve the technical problems, the invention provides a bisphenol A production method and device which can effectively reduce the content of impurities such as 2, 4-bisphenol A and the like in the device, greatly reduce the impurity amount returned to a reaction unit and reduce or even cancel heavy residue discharge.
The production method of the invention comprises the following steps:
step A: in the presence of an acid catalyst, carrying out condensation reaction on excessive phenol and acetone to obtain a reaction mixed solution containing bisphenol A;
and (B) step (B): concentrating the reaction mixed solution obtained in the step A to obtain a concentrated solution;
step C: crystallizing the concentrated solution obtained in the step B, then carrying out solid-liquid separation, wherein the solid component is an adduct containing 4, 4-bisphenol A and phenol, and further separating and removing the phenol to obtain bisphenol A; the liquid component is mother liquor I;
step D: carrying out isomerization treatment on the mother liquor I obtained in the step C, continuing to separate, and respectively obtaining an adduct filter cake of phenol and 4, 4-bisphenol A and a mother liquor II again;
step E: and D, reacting the mother liquor II obtained in the step D with an epoxy compound to obtain the byproduct polyphenol epoxy resin.
The following describes the above steps further, and in step A, the synthesis of bisphenol A comprises the following reactions: and (3) reacting phenol with acetone to generate bisphenol A and generating byproduct polyphenol impurities such as 2, 4-bisphenol A, triphenol, tetraphenol, chroman and the like.
The purpose of the step B is to concentrate the reaction product of the step A, and materials such as low boiling point water, acetone and the like are removed in the concentration process. Wherein, the acetone can be recovered, and the recovered acetone can be returned to the step A or used for other purposes.
In step C, the crystallization method may be selected from methods conventional in the art, such as suspension crystallization, falling film crystallization, vacuum crystallization, static crystallization, evaporative crystallization, etc., or a combination of two or more crystallization methods. The crystallized product is separated through solid-liquid separation to obtain solid component containing the adduct of bisphenol A and phenol and mother liquid I. The common methods for the solid-liquid separation step comprise vacuum filtration, centrifugal separation and the like; meanwhile, in operation, the purity of the adduct filter cake of phenol and 4, 4-bisphenol A can be further improved and the impurity content is reduced by the washing operation of washing liquid (phenol or the adduct filter cake of the previous stage of solid-liquid separation is washed by adopting mother liquor after the subsequent stage of crystallization and solid-liquid separation and the washing liquid). Alternatively, phenol may be recovered as the solid component is removed, and the recovered phenol may be returned to step a or otherwise utilized.
The researchers find that impurities (byproduct polyphenol impurities) in the bisphenol A production process can be used as raw materials to prepare the polyphenol epoxy resin, so that waste is changed into valuable, the emission of heavy residues can be reduced or canceled, the energy consumption is reduced, the obtained mother liquor is subjected to isomerization treatment before the polyphenol epoxy resin is prepared, the yield of bisphenol A can be further improved, and the steps D and E are further arranged.
Preferably, said mother liquor II obtained in said D has a phenol content of less than 7wt%, preferably less than 6wt%, more preferably less than 4wt%;
as a preferred mode of operation, phenol is removed by concentration when the phenol content in the mother liquor II is higher than 7% by weight.
Alternatively, the phenol removed in this step may be recovered and the recovered phenol may be returned to step A or otherwise utilized.
Preferably, in the step D, the isomerization treatment means: after the mother liquor I is isomerized, a mixed solution containing 11.3-13wt% of 4, 4-bisphenol A, 1.9-2.2wt% of 2, 4-bisphenol A isomer and phenol and other impurities is obtained.
In the step D, the main components of the mother liquor I include: 9.8-10wt% of 4, 4-bisphenol A, 3.3-3.5wt% of 2, 4-bisphenol A isomer, phenol and other polyphenol impurities.
As a preferred mode of operation, the isomerisation is carried out under the influence of a catalyst cation exchange resin.
As a preferred mode of operation, the isomerised compound is further concentrated to give a mixed solution containing 25-26wt% of 4, 4-bisphenol A, 4.2-4,4wt% of the 2, 4-bisphenol A isomer, phenol and other impurities.
As a preferred mode of operation, the concentrated solution is continuously crystallized, 4-bisphenol a is precipitated by forming adduct crystals with phenol, and the filter cake (or filter residue) is washed with phenol liquid by solid-liquid separation to obtain a phenol-4, 4-bisphenol a adduct filter cake and a mother liquor II mainly containing by-product polyphenol.
Preferably, the reaction in step E specifically includes: in the presence of a phase transfer catalyst quaternary ammonium salt, the mother solution II reacts with an epoxy compound to obtain an etherification product, and then reacts with alkali to obtain the epoxy resin.
Preferably, the quaternary ammonium salt of the phase transfer catalyst is benzyl triethyl ammonium chloride;
preferably, the epoxy compound is epichlorohydrin, beta-methyl-epichlorohydrin;
preferably, the base is an aqueous sodium hydroxide solution.
Preferably, the step D further comprises the step of washing and refining the obtained crude epoxy resin product, removing the solvent, and further obtaining the finished epoxy resin product.
According to the need, the preparation method of bisphenol A further comprises a step F of carrying out catalytic decomposition treatment on part of the mother liquor II obtained in the step D, recovering phenol and/or 4-isopropenylphenol obtained after the decomposition, and discharging heavy residues generated by the decomposition.
Under the condition that the byproduct polyphenol cannot be completely digested in the epoxy step, transferring the concentrated mother liquor II into a conventional catalytic cracking treatment step, and recovering the effective components. The generation and discharge of solid waste, especially heavy residues, is also effectively reduced.
The heavy residues typically include heavy compounds such as chromans that are converted to non-volatile.
Preferably, the decomposing specifically includes: under the conditions of catalytic alkali and high temperature, the polyhydric phenol in the mother solution II is catalytically decomposed into recoverable phenol and 4-isopropenylphenol;
preferably the catalytic base is selected from NaOH and NaHCO 3 、NaH 2 PO 4 One or more mixtures thereof.
Preferably, the recovered phenol is returned to step A, or alternatively, the phenol is subjected to a rearrangement reaction with 4-isopropenylphenol to produce 4, 4-bisphenol A, and 4, 4-bisphenol A is recovered.
Preferably, the catalyst for the rearrangement reaction is a cation exchange resin catalyst;
preferably, the cation exchange resin catalystThe chemical agent is prepared by the following method: styrene and divinylbenzene are adopted for crosslinking, and the sulfonation reaction of sulfuric acid is added to prepare the belt-SO 3 A base resin of H functional groups; modifying it with promoter to make a part of-SO 3 H functional group is modified into sulfhydryl group, thus obtaining the-SO-containing 3 H and mercapto bifunctional catalysts.
The accelerator is preferably mercaptoethylamine (mercaptoalkylamine species).
The invention also provides a bisphenol A production device for realizing the method, which comprises the following steps: the device comprises a reaction unit, a concentration unit, a crystallization unit, a solid-liquid separation unit, an isomerization unit, a mother liquor evaporation unit and an epoxy resin production unit which are connected in sequence; the isomerization unit comprises isomerization reaction equipment, concentration equipment, crystallization equipment and solid-liquid separation equipment which are connected in sequence.
Optionally, the production device further comprises a decomposition unit, a heavy residue removal unit and a raw material recovery unit connected with the decomposition unit.
The beneficial effects of the invention are as follows:
in the bisphenol A production process described in the prior art such as CN104379546A, heavy residues are generated, and the discharge amount of the heavy residues reflects the loss of materials and energy of the process. By adopting the method, the mother liquor II is used as the raw material for producing the byproduct polyphenol epoxy resin, so that the generation of heavy residues of the decomposition process in the bisphenol A process is eliminated or at least greatly reduced, and the method has great benefits on environmental protection and energy consumption reduction. In addition, the isomerization process reduces the generation of 2, 4-bisphenol A byproducts, improves the production, reduces the consumption (efficiency enhancement) of raw materials of phenol and acetone, reduces the manufacturing cost of products, and improves the technical level of devices.
The calculated polyphenol discharge amount is about 2955 tons/year, the phenol unit consumption is about 842.3kg/t, the acetone unit consumption is about 271.6kg/t, and the energy consumption in all aspects is huge; after the method is adopted, the content of 2, 4-bisphenol A in the device is greatly reduced; meanwhile, the emission of heavy residues can be completely canceled or partially reduced, so that the consumption (synergistic effect) of raw materials of phenol and acetone is reduced, the manufacturing cost of the product is reduced, the technical advantages of product manufacturing are reflected, and the technical level of the device is improved.
Drawings
FIG. 1 is a process flow diagram of the bisphenol A production process of the present invention.
Fig. 2 is a process flow diagram of the process for the preparation of bisphenol a disclosed in CN104379546 a.
Detailed Description
The following examples are illustrative of the invention and are not intended to limit the scope of the invention.
Wherein:
BPA molecular structural formula:
2,4-BPA molecular structural formula:
one of the molecular structural formulas of C3 phenol:
the triphenol is a triphenol with one of the molecular structural formulas
The tetraphenol is tetraphenol, and has one of its molecular structural formulas
One of the molecular structural formulas of chromans
Example 1
The embodiment provides a method for producing bisphenol A, which comprises the following steps:
step A: in the presence of an acid catalyst, carrying out condensation reaction on excessive phenol and acetone to generate bisphenol A, so as to obtain a reaction mixed solution containing bisphenol A;
and (B) step (B): dehydrating and concentrating the reaction mixed solution obtained in the step A to obtain a dehydrated concentrated solution;
step C: crystallizing the dehydrated concentrate obtained in the step B, and then performing solid-liquid separation to obtain a solid component containing an adduct of bisphenol A and phenol and a mother liquor I;
step D: feeding mother liquor I with the flow rate of 12t/h and containing 10wt% of 4, 4-bisphenol A, 3.3wt% of 2, 4-bisphenol A isomer and phenol and other impurities into an isomerization reactor, and carrying out isomerization reaction to obtain bisphenol A solution with the flow rate of 12t/h and containing 11.3wt% of 4, 4-bisphenol A, 1.9wt% of 2, 4-bisphenol A isomer and phenol and other impurities;
sending the mixture into a concentration unit to remove phenol to obtain mixed liquid with the flow rate of 5.42t/h, 25wt% of 4, 4-bisphenol A, 4.2wt% of 2, 4-bisphenol A isomer and other impurities;
performing crystallization cooling, conveying a solid-liquid phase mixed solution containing phenol-4, 4 bisphenol A adduct crystals into a solid-liquid separator for solid-liquid separation operation, and washing with phenol solution with the concentration of 1.35t/h and phenol of 99.9wt% to obtain a filter cake and mother liquor II;
step E: the mother liquor II (the flow rate is 5.08t/h, the content of 4, 4-bisphenol A is 10wt%, the content of 2, 4-bisphenol A isomer is 4.15wt%, phenol and other impurities are added into a phenol evaporation unit in the bisphenol A production process, and after dephenolization, a mixed solution with the flow rate of 1.19t/h, the content of phenol is 5wt%, the content of 4, 4-bisphenol A is 42.6wt%, the content of 2, 4-bisphenol A isomer is 17.68wt% and other impurities is obtained);
and (3) all the obtained mixed solution is sent into an epoxy resin production line, dissolved in excessive epoxy chloropropane, added with a phase transfer catalyst, heated to about 100 ℃ for etherification reaction, cooled to about 55 ℃, and dropwise added with 48% NaOH aqueous solution for ring closure reaction. And (3) after the reaction is finished, recovering excessive epichlorohydrin to obtain epoxy resin crude resin, adding toluene solvent, adding water to carry out refining and desalting, and finally removing the solvent to obtain an epoxy resin finished product.
It was calculated that approximately 1.35 tons of epoxy resin could be produced per 1 ton of mixed liquor consumed. Annual epoxy resin yield is 12852 tons (calculated as 1.35 tons of epoxy resin produced from 1 ton of mixed solution and 8000 hours per year).
And D, heating and melting the filter cake to obtain bisphenol A solution with the flow rate of 1.69t/h, the content of 50wt% of 4, 4-bisphenol A, the content of 1wt% of 2, 4-bisphenol A isomer and the other content of phenol and trace impurities, and returning the bisphenol A solution to a filter cake tank before a crystallization unit in the bisphenol A production process or after solid-liquid separation in the bisphenol A production process.
Example 2
The same production method as in example 1 was employed, except that:
step E: the mother liquor II obtained was fed into a phenol evaporation unit, and after dephenolization, a mixed solution was obtained having a flow rate of 1.19t/h and containing 5% by weight of phenol, 42.6% by weight of 4, 4-bisphenol A, and 17.68% by weight of the 2, 4-bisphenol A isomer.
A part of the resulting mixed solution was fed into an epoxy resin production line at a flow rate of 0.6t/h, for a specific production method, see example 1.
Annual epoxy resin production of 6480 tons (calculated as 1.35 tons of epoxy resin produced from 1 ton of mixed solution and 8000 hours per year) was calculated.
The rest mixed solution is subjected to catalytic decomposition treatment (namely step F) at the flow rate of 0.59t/h, and the method reduces 1650 tons of heavy residue emission in the year.
Example 3
The same production method as in example 1 was employed, except that:
step D: feeding a mother solution I with the flow rate of 14t/h and containing 9.8wt% of 4, 4-bisphenol A, 3.5wt% of 2, 4-bisphenol A isomer and phenol and other impurities into an isomerization reactor, and carrying out isomerization reaction to obtain a bisphenol A solution with the flow rate of 14t/h and containing 13wt% of 4, 4-bisphenol A, 2.2wt% of 2, 4-bisphenol A isomer and phenol and other impurities;
sending the mixture into a concentration unit to remove phenol to obtain mixed liquid with the flow rate of 7t/h, 26wt% of 4, 4-bisphenol A, 4.4wt% of 2, 4-bisphenol A isomer and other impurities;
performing crystallization cooling, conveying a solid-liquid phase mixed solution containing phenol-4, 4 bisphenol A adduct crystals into a solid-liquid separator for separation operation, and washing with phenol with the concentration of 1.94t/h and phenol with the concentration of 99.9wt% to obtain a filter cake and a mother liquor II;
step E: the mother solution II (the flow rate is 6.51t/h, the content of 4, 4-bisphenol A is 10wt%, the content of 2, 4-bisphenol A isomer is 4.43wt%, phenol and other impurities are added into a phenol evaporation unit, and after dephenolization, a mixed solution of polyhydric phenols such as 1.54t/h, the content of phenol is 5wt%, 4-bisphenol A is 42.28wt%, the content of 2, 4-bisphenol A isomer is 14.3wt% and other ternary and quaternary phenols are obtained;
all the obtained mixed solution is sent into an epoxy resin production line, and 16632 tons of epoxy resin can be produced annually (1.35 tons of epoxy resin are produced according to 1 ton of mixed solution, and the annual production time is 8000 hours);
and (D) heating and melting the filter cake obtained in the step (D) to obtain bisphenol A solution with the flow rate of 2.43t/h, the content of 48wt% of 4, 4-bisphenol A, the content of 0.8wt% of 2, 4-bisphenol A isomer and the other content of phenol and trace impurities, and returning the bisphenol A solution to the front of a crystallization unit of the main process flow.
Example 4
An apparatus (schematic view of which is shown in FIG. 1) for carrying out the bisphenol A production of examples 1-3 above, comprising: the device comprises a reaction unit, a concentration unit (dehydration unit), a crystallization unit, a solid-liquid separation I unit, an isomerization unit, a mother liquor concentration unit and an epoxy resin production unit which are connected in sequence;
the isomerization unit also comprises isomerization reaction equipment, concentration crystallization equipment and solid-liquid separation II equipment.
The production device also comprises a decomposition unit and a rearrangement unit connected with a discharge port pipeline of the decomposition unit; the feed inlet of the decomposition unit is connected with the discharge outlet of the mother liquor concentration unit in a pipeline manner, and the discharge outlet of the rearrangement unit is connected with the feed inlet of the reaction unit in a pipeline manner.
While the invention has been described in detail in the foregoing general description and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that modifications and improvements can be made thereto. Accordingly, such modifications or improvements may be made without departing from the spirit of the invention and are intended to be within the scope of the invention as claimed.
Claims (14)
1. A process for producing bisphenol a, comprising:
step A: in the presence of an acid catalyst, carrying out condensation reaction on excessive phenol and acetone to obtain a reaction mixed solution containing bisphenol A;
and (B) step (B): concentrating the reaction mixed solution obtained in the step A to obtain a concentrated solution;
step C: crystallizing the concentrated solution obtained in the step B, then carrying out solid-liquid separation, wherein the solid component is an adduct containing 4, 4-bisphenol A and phenol, and further separating and removing the phenol to obtain bisphenol A; the liquid component is mother liquor I;
step D: carrying out isomerization treatment on the mother liquor I obtained in the step C, and continuously separating again to obtain an adduct filter cake of phenol and 4, 4-bisphenol A and a mother liquor II respectively; the isomerization treatment refers to: isomerizing the mother solution I to obtain a mixed solution containing 11.3-13wt% of 4, 4-bisphenol A, 1.9-2.2wt% of 2, 4-bisphenol A isomer and phenol and other impurities; the content of phenol in the mother liquor II is not higher than 7wt%;
step E: and D, reacting the mother liquor II obtained in the step D with an epoxy compound to obtain the byproduct polyphenol epoxy resin.
2. The production method according to claim 1, wherein the phenol content in the mother liquor II is less than 6wt%.
3. The production method according to claim 2, characterized in that the phenol content in the mother liquor II is lower than 4wt%.
4. The production method according to claim 2, characterized in that phenol is removed by concentration when the phenol content in the mother liquor II is higher than 7 wt%.
5. The process according to any one of claims 1 to 4, wherein in step D the isomerisation is carried out under the influence of a catalytic cation exchange resin.
6. The method according to any one of claims 1 to 4, wherein the reaction in step E specifically comprises: in the presence of a phase transfer catalyst quaternary ammonium salt, the mother solution II reacts with an epoxy compound to obtain an etherified product, and then reacts with alkali to obtain the byproduct polyphenol epoxy resin.
7. The production method according to claim 6, wherein the quaternary ammonium salt of the phase transfer catalyst is benzyl triethyl ammonium chloride;
and/or the epoxy compound is one or two of epichlorohydrin and beta-methyl-epichlorohydrin;
and/or the base is provided as an aqueous solution of one or more of sodium hydroxide, calcium hydroxide, or potassium hydroxide.
8. The method according to claim 7, wherein the alkali is an aqueous sodium hydroxide solution.
9. The production method according to any one of claims 1 to 4, further comprising step F: and D, carrying out catalytic decomposition treatment on part of the mother liquor II obtained in the step D, recovering phenol and/or 4-isopropenylphenol generated after decomposition, and discharging heavy residues generated by decomposition.
10. The production method according to claim 9, wherein the decomposing specifically comprises: and under the conditions of catalytic alkali and high temperature, the polyhydric phenol in the mother solution II is catalytically decomposed into recoverable phenol and 4-isopropenylphenol.
11. The method according to claim 10, wherein the catalytic base is NaOH or NaHCO 3 、NaH 2 PO 4 One or more mixtures thereof.
12. The process according to claim 9, wherein the phenol recovered in step F is recycled to step a, or phenol is subjected to a rearrangement reaction with 4-isopropenylphenol to produce and recover 4, 4-bisphenol a.
13. The production method according to claim 1, wherein the production apparatus employed in the production method comprises: the device comprises a reaction unit, a concentration unit, a crystallization unit, a solid-liquid separation unit, an isomerization unit, a mother liquor evaporation unit and an epoxy resin production unit which are connected in sequence; the isomerization unit comprises isomerization reaction equipment, concentration equipment, crystallization equipment and solid-liquid separation equipment which are connected in sequence.
14. The production method according to claim 13, wherein the production apparatus further comprises a decomposition unit, a heavy residue removal unit, and a raw material recovery unit connected to the decomposition unit.
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| CN116410060A (en) * | 2021-12-31 | 2023-07-11 | 南通星辰合成材料有限公司 | Method for inhibiting generation of impurity isopropenylphenol in bisphenol A synthesis process |
| CN116041668A (en) * | 2022-10-27 | 2023-05-02 | 江苏扬农锦湖化工有限公司 | Method for preparing epoxy resin by using bisphenol F mother liquor |
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