CN109574835A - A kind of method of ion modification activity carbon decoloring polyesterols solution product BHET - Google Patents
A kind of method of ion modification activity carbon decoloring polyesterols solution product BHET Download PDFInfo
- Publication number
- CN109574835A CN109574835A CN201811384512.7A CN201811384512A CN109574835A CN 109574835 A CN109574835 A CN 109574835A CN 201811384512 A CN201811384512 A CN 201811384512A CN 109574835 A CN109574835 A CN 109574835A
- Authority
- CN
- China
- Prior art keywords
- ion
- bhet
- polyester
- active carbon
- discoloration
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C07C67/56—Separation; Purification; Stabilisation; Use of additives by solid-liquid treatment; by chemisorption
Abstract
The invention discloses the methods of ion modification activity carbon decoloring polyesterols solution product BHET a kind of, belong to offal treatment and environmental protection technical field.Ion modification is carried out to active carbon using ferrous ion, ferric ion or trivalent aluminium ion, to improve its absorption property to dyestuff contained in BHET, it can be used for the decolorization of polyester alcoholysis product terephthalic acid glycol ester (BHET), the purity for improving BHET, is conducive to the cycling and reutilization of polyester.The method of the present invention have can omit calcination process process, at low cost, high-efficient, easy to operate, reusable advantage.
Description
Technical field
The present invention relates to the methods of ion modification activity carbon decoloring polyesterols solution product BHET a kind of, belong to offal treatment
And environmental protection technical field.
Background technique
Polyester (PET) is one of the polymer being most often used at present, however, with the increase of PET usage amount, it can not
Biodegradable characteristic makes it recycle the big focus for becoming environmental protection.Glycolysis alcoholysis method is industrial circle and
Art circle is widely adopted one of polyester chemistry recovery method, i.e., is under certain condition dropped PET by using excessive ethylene glycol
Solution is monomer molecule or oligomer, then is prepared into the various polymer with application value, such as textile dyestuff, poly- ammonia
Ester foam, epoxy curing agent etc..But studies have shown that dyestuff contained in polyester product, pigment etc. will affect polyesterols
The color and purity of product are solved, and then limits recycling for polyester alcoholysis product.
Have the report handled using ion modification active carbon waste water at present, but is substantially used to handle waste water
In metal ion or organic compound, such as heavy metal arsenic, fluoride, cyanide.The principle of this modification is to pass through load
Metal ion improves the catalysis oxidation ability of active carbon, and forms it with the substance in waste water by loading respective metal ion
Complex compound is to improve suction-operated of the active carbon to harmful substance.It is basic without using ion modification but in these reports
Active carbon handles the cases of Wastewater Dyes.In view of polyester catabolite BHET can be completely dissolved in the hot water, contained by
Dyestuff can be also uniformly distributed in the solution, this enables the decoloration to BHET to complete in liquid-phase system.Some conventional waste water
Chemical decolorization method principle, which is substantially, is destroyed dye molecule using Strong oxdiative substance, thus realize the decoloration to waste water, and
As organic matter, oxidizing process can be also oxidized BHET sheet while oxidation dye molecule, so that realizing to BHET solution de-
After color, BHET also disappears therewith.Therefore, seek a kind of feasible, efficient, economic, convenient and fast method, Lai Shixian polyester alcoholysis produces
Effective decoloration of object-ethylene glycol terephthalate (BHET) is problem urgently to be resolved in PET cycling and reutilization.
Summary of the invention
In order to solve deficiency present in existing polyester alcoholysis product BHET decoloration and recycle utilization, the present invention is adopted
Adsorption bleaching is carried out to it with ion modification active carbon, enhances active carbon specific surface area, to improve adsorption bleaching efficiency.
The first purpose of the invention is to provide the discoloration method of polyester alcoholysis product BHET a kind of, the method is to utilize
Ion modification active carbon and polyester alcoholysis product ultrasonic mixing carry out decolorization adsorption.
In one embodiment of the invention, the ion includes ferrous ion, ferric ion, in trivalent aluminium ion
It is one or more.
In one embodiment of the invention, the ion modification activated carbon weight content is not less than BHET weight content
5%.
In one embodiment of the invention, the preparation method of the ion modification active carbon includes: according to a mole matter
Ratio is measured, the ion source of 0.2-20moL is mixed with the active carbon of 100-1000g, obtains ion modification active carbon.
In one embodiment of the invention, the ion source of the ion include the corresponding hydrochloride of ion, nitrate,
One of sulfate, phosphate are a variety of.
In one embodiment of the invention, the ultrasound be in 80~100Hz ultrasonic cleaner ultrasound 1~
8h。
In one embodiment of the invention, the ion modification method for preparation of active carbon further include mixing after stand,
Cross from, it is dry.
In one embodiment of the invention, the ion modification method for preparation of active carbon specifically includes: according to mole
Mass ratio mixes ion source with active carbon, mixed liquor is placed in 1~8h of ultrasound in 80~100Hz ultrasonic cleaner, so
Afterwards under normal temperature condition stand dipping 12~for 24 hours.After reaction, mixed liquor is separated by filtration, and will be modified with deionized water
Active carbon repeated flushing to pH 6.8~7.2, be put into 50~70 DEG C of blast dry oven drying to constant weight to get to ferrous iron
Ion modification active carbon.
In one embodiment of the invention, the discoloration method of the polyester alcoholysis product BHET includes: according to weight
Polyester alcoholysis product BHET and ion modification active carbon are mixed in hot water by proportion, after filtering, cooling are up to decolourizing
BHET。
In one embodiment of the invention, the temperature of the hot water is 80-95 DEG C.
In one embodiment of the invention, the discoloration method of the polyester alcoholysis product BHET specifically includes: according to
Polyester alcoholysis product BHET is dissolved in 10~50L, 80~95 DEG C of hot water by weight proportion, and ferrous ion modified active is added
Charcoal, concussion are decolourized after 1~3h, filter mixed liquor, the BHET aqueous solution after being decolourized, the BHET after being recrystallized to give decoloration
Solid crystal.
A second object of the present invention is to provide a kind of polyester recovery method, the method is by glycolysis alcoholysis, so
After decolourize, obtain polyester recycling product；The decoloration is carried out using above-mentioned discoloration method.
Beneficial effects of the present invention:
1, the adsorption bleaching of polyester alcoholysis product BHET may be implemented in the ion modification active carbon of preparation method of the present invention, uses
It is handled in the cycling and reutilization of polyester alcoholysis product BHET, calcination process process, at low cost, high-efficient, operation can be omitted by having
Easy, reusable advantage.
2, the decoloration performance of the ion modification active carbon of preparation method of the present invention preferably, transitory efficient, 2h takes off BHET
Color rate reaches as high as the average percent of decolourization in 100%, 2h and reaches as high as 93.67%；And used ion modification active carbon
It may be implemented to regenerate, can be recycled, and the ion modification active carbon after 5 repetitions are adsorbed still may be used to the percent of decolourization of BHET
Reach 71.11%.
Specific embodiment
Below with reference to test example and specific embodiment, the present invention is described in further detail.But this should not be understood
It is all that this is belonged to based on the technology that the content of present invention is realized for the scope of the above subject matter of the present invention is limited to the following embodiments
The range of invention.
Modified activated carbon specific surface area and hole hold measuring method: weighing the ion modification activity carbon sample that quality is about 0.15g
Product after pretreatment 6h removes moisture and air in sample, measure specific surface area, the hole of sample under the conditions of liquid nitrogen (- 196 DEG C)
Hold, BET method is respectively adopted in the specific surface area of sample, Kong Rong and BJH method is calculated.
Adsorption bleaching rate measuring method: when adsorption time is 2h, sampling interval 10min, when adsorption time is 12h,
Sampling interval is 30min.The absorbance of 12 sample points is measured by ultraviolet spectra and is calculated in solution by standard curve
The concentration of dyestuff, Dye Removal rate are calculated by following formula
Wherein, C0For dyestuff initial concentration, C in solutiontFor dye strength in t moment solution, Y is percent of decolourization.Final decoloration
Rate is the percent of decolourization of the 12nd sample point, and the average percent of decolourization in 2h is the average value of 12 sample point percent of decolourizations.
Adsorption bleaching of the 1 ferrous ion modified activated carbon of embodiment to polyester alcoholysis product BHET
(1) preparation of ferrous ion modified activated carbon: weighing 100g active carbon, and the concentration for being added to 1L is 0.8mol/L's
FeSO4·7H2In O solution, mixed liquor is placed in ultrasound 4h in 100Hz ultrasonic cleaner, dipping is then stood under normal temperature condition
24h.After reaction, mixed liquor is separated by filtration, and modified active carbon repeated flushing to pH is existed with deionized water
7.0, it is put into 70 DEG C of blast dry oven drying to constant weight to get to ferrous ion modified activated carbon, be sealed
(2) 100g polyester alcoholysis product BHET ferrous ion modified activated carbon adsorption bleaching BHET: is dissolved in 10L 90
In DEG C hot water, it is added the ferrous ion modified activated carbon of 100g, after concussion decoloration 2h, filter mixed liquor, after being decolourized
BHET aqueous solution, the BHET solid crystal after being recrystallized to give decoloration.
Using ferrous ion modified activated carbon specific surface area 1229.15m manufactured in the present embodiment2/ g, total pore volume 0.41cm2/
100% is reached as high as i.e. up to 93.67% to the average adsorption percent of decolourization of polyester alcoholysis product BHET in g, 2h.
Adsorption bleaching of the 2 ferrous ion modified activated carbon of embodiment to polyester alcoholysis product BHET
Referring to embodiment 1, the ultrasonic time in step (1) is changed to 8h, other conditions are constant, and ferrous ion is prepared
Modified activated carbon；And gained ferrous ion modified activated carbon decolourizes according to the method condition in embodiment 1, obtain BHET
Solid crystal.
Using ferrous ion modified activated carbon specific surface area 1163.56m manufactured in the present embodiment2/ g, total pore volume 0.39cm2/
Bleaching time is extended, percent of decolourization is reachable i.e. up to 91.18% to the average adsorption percent of decolourization of polyester alcoholysis product BHET in g, 2h
100%.
Adsorption bleaching of the 3 ferrous ion modified activated carbon of embodiment to polyester alcoholysis product BHET
Referring to embodiment 1, the ultrasonic time in step (1) is changed to 1h, other conditions are constant, and ferrous ion is prepared
Modified activated carbon；And gained ferrous ion modified activated carbon decolourizes according to the method condition in embodiment 1, obtain BHET
Solid crystal.
Using ferrous ion modified activated carbon specific surface area 1143.09m manufactured in the present embodiment2/ g, total pore volume 0.37cm2/
Bleaching time is extended up to 88.05% to the average adsorption percent of decolourization of polyester alcoholysis product BHET in g, 2h, percent of decolourization is reachable
100%.
Adsorption bleaching of the 4 ferrous ion modified activated carbon of embodiment to polyester alcoholysis product BHET
Referring to embodiment 3, by the FeSO in step (1)4·7H2O concentration is changed to 1.6mol/L, and other conditions are constant, preparation
Obtain ferrous ion modified activated carbon；And gained ferrous ion modified activated carbon is carried out according to the method condition in embodiment 1
Decoloration, obtains BHET solid crystal.
Using ferrous ion modified activated carbon specific surface area 1166.27m manufactured in the present embodiment2/ g, total pore volume 0.37cm2/
Bleaching time is extended up to 87.13% to the average adsorption percent of decolourization of polyester alcoholysis product BHET in g, 2h, percent of decolourization is reachable
100%.
Adsorption bleaching of the 5 ferrous ion modified activated carbon of embodiment to polyester alcoholysis product BHET
Referring to embodiment 1, the modified activated carbon dosage in step (2) is changed to 5% (50g modified activated carbon: 1000 alcoholysis
Product BHET), other conditions are constant, decolourize to BHET, obtain BHET solid crystal.
Using ferrous ion modified activated carbon manufactured in the present embodiment, average adsorption of the 12h to polyester alcoholysis product BHET
Percent of decolourization extends bleaching time, percent of decolourization is up to 100% up to 86.24%.
Adsorption bleaching of the 6 ferric ion modified activated carbon of embodiment to polyester alcoholysis product BHET
Referring to embodiment 1, ferrous ion is only replaced with into ferric ion, other conditions are constant, and ferric iron is prepared
Ion modification active carbon；And gained ferric ion modified activated carbon is taken off according to the condition of step (2) in embodiment 1
Color obtains BHET solid crystal.
Using ferric ion modified activated carbon specific surface area 1153.44m manufactured in the present embodiment2/ g, total pore volume
0.40cm2/ g, 2h are to extend bleaching time, percent of decolourization can up to 87.69% to the adsorption bleaching rate of polyester alcoholysis product BHET
Up to 100%.
Adsorption bleaching of the 7 trivalent aluminium ion modified activated carbon of embodiment to polyester alcoholysis product BHET
Referring to embodiment 1, ferrous ion is only replaced with into trivalent aluminium ion, other conditions are constant, and trivalent aluminium is prepared
Ion modification active carbon；And gained trivalent aluminium ion modified activated carbon is taken off according to the condition of step (2) in embodiment 1
Color obtains BHET solid crystal.
Using trivalent aluminium ion modified activated carbon specific surface area 1184.34m manufactured in the present embodiment2/ g, total pore volume
0.38cm2/ g, 2h are to extend bleaching time, percent of decolourization can up to 90.69% to the adsorption bleaching rate of polyester alcoholysis product BHET
Up to 100%.
Reference examples 1:
Referring to 1 step of embodiment (2) condition, the active carbon of ion modification is replaced with into unmodified pure active carbon, other
Condition is constant, decolourizes to BHET, obtains decoloration BHET solid crystal.
75% is up to using adsorption bleaching rate of this method to polyester alcoholysis product BHET.
Reference examples 2:
Referring to embodiment 1, the ultrasonic step in step (1) is replaced with into mechanical stirring, other conditions are constant, are prepared
Ferrous ion modified activated carbon；And gained ferrous ion modified activated carbon is taken off according to the condition of step (2) in embodiment 1
Color obtains BHET solid crystal.
Using ferrous ion modified activated carbon specific surface area 512.56m manufactured in the present embodiment2/ g, total pore volume 0.24cm2/
G, 2h only have 56.15% to the adsorption bleaching rate of polyester alcoholysis product BHET.
Claims (10)
1. a kind of discoloration method of polyester alcoholysis product BHET, which is characterized in that the method is to utilize ion modification active carbon
With polyester alcoholysis product ultrasonic mixing, adsorption bleaching is carried out.
2. discoloration method according to claim 1, which is characterized in that the ion include ferrous ion, ferric ion,
It is one or more in trivalent aluminium ion.
3. discoloration method according to claim 1, which is characterized in that the ion modification activated carbon weight content is not less than
The 5% of BHET weight content.
4. discoloration method according to claim 1, which is characterized in that the preparation method packet of the ion modification active carbon
It includes: according to molal weight ratio, the ion source of 0.2-20moL being mixed with the active carbon of 100-1000g, obtain ion modification activity
Charcoal.
5. discoloration method according to claim 4, which is characterized in that the ion source include the corresponding hydrochloride of ion,
One of nitrate, sulfate, phosphate are a variety of.
6. discoloration method according to claim 1, which is characterized in that the ultrasound is in 80~100Hz ultrasonic cleaning
It is carried out in device.
7. discoloration method according to claim 4 or 5, which is characterized in that the ion modification method for preparation of active carbon is also
Including stand, cross after mixing from, it is dry.
8. -7 any discoloration method according to claim 1, which is characterized in that the method specifically includes: according to weight
Polyester alcoholysis product BHET and ion modification active carbon are mixed in hot water by proportion, after filtering, cooling are up to decolourizing
BHET。
9. discoloration method according to claim 8, which is characterized in that the temperature of the hot water is 80-95 DEG C.
10. a kind of polyester recovery method, which is characterized in that the method is then decolourized, obtained by glycolysis alcoholysis
Polyester recycles product；The decoloration is carried out using any discoloration method of claim 1-9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811384512.7A CN109574835B (en) | 2018-11-20 | 2018-11-20 | Method for decoloring polyester alcoholysis product BHET (BHET) by using ion modified activated carbon |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811384512.7A CN109574835B (en) | 2018-11-20 | 2018-11-20 | Method for decoloring polyester alcoholysis product BHET (BHET) by using ion modified activated carbon |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109574835A true CN109574835A (en) | 2019-04-05 |
| CN109574835B CN109574835B (en) | 2021-01-29 |
Family
ID=65923020
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811384512.7A Active CN109574835B (en) | 2018-11-20 | 2018-11-20 | Method for decoloring polyester alcoholysis product BHET (BHET) by using ion modified activated carbon |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109574835B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112174781A (en) * | 2020-11-05 | 2021-01-05 | 艾凡佳德(上海)环保科技有限公司 | Method and equipment for decoloring ethylene glycol |
| CN113562905A (en) * | 2020-04-28 | 2021-10-29 | 宝山钢铁股份有限公司 | High-salinity wastewater advanced treatment method and system |
| WO2023228034A1 (en) * | 2022-05-23 | 2023-11-30 | Ingbiocomb Sas | Catalyst and process for obtaining bhet from pet |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774153A (en) * | 2014-01-15 | 2015-07-15 | 中国科学院过程工程研究所 | Recycling method for catalytic degradation of waste PET |
| US9499414B1 (en) * | 2015-04-30 | 2016-11-22 | King Fahd University Of Petroleum And Minerals | Method of dye removal from wastewater |
-
2018
- 2018-11-20 CN CN201811384512.7A patent/CN109574835B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104774153A (en) * | 2014-01-15 | 2015-07-15 | 中国科学院过程工程研究所 | Recycling method for catalytic degradation of waste PET |
| US9499414B1 (en) * | 2015-04-30 | 2016-11-22 | King Fahd University Of Petroleum And Minerals | Method of dye removal from wastewater |
Non-Patent Citations (2)
| Title |
|---|
| 刘超等: "活性炭改性方法的研究进展", 《化学工程与装备》 * |
| 郭连杰等: "金属离子改性活性炭对分离ＣＨ４／Ｎ２", 《化工进展》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113562905A (en) * | 2020-04-28 | 2021-10-29 | 宝山钢铁股份有限公司 | High-salinity wastewater advanced treatment method and system |
| CN113562905B (en) * | 2020-04-28 | 2023-11-14 | 宝山钢铁股份有限公司 | Advanced treatment method and system for high-salinity wastewater |
| CN112174781A (en) * | 2020-11-05 | 2021-01-05 | 艾凡佳德(上海)环保科技有限公司 | Method and equipment for decoloring ethylene glycol |
| WO2023228034A1 (en) * | 2022-05-23 | 2023-11-30 | Ingbiocomb Sas | Catalyst and process for obtaining bhet from pet |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109574835B (en) | 2021-01-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109574835A (en) | A kind of method of ion modification activity carbon decoloring polyesterols solution product BHET | |
| CN108620125A (en) | A kind of preparation method of the nitridation carbon complex with high catalytic degradation activity | |
| CN108940237B (en) | Preparation method and application of magnetic adsorption material | |
| CN107715855B (en) | It is a kind of for organic dyestuff and the porous carbon materials of fluoride wastewater treatment and preparation method thereof | |
| CN110694662B (en) | Two-dimensional I-doped BiOIO 3 /g-C 3 N 4 Composite catalyst and preparation method and application thereof | |
| CN103861571B (en) | The preparation method of polyaniline composite titanium dioxide adsorbent, application and renovation process | |
| CN112808226A (en) | Aluminum-based lithium ion sieve and preparation method and application thereof | |
| CN106861622A (en) | A kind of water treatment agent for processing eutrophication water | |
| CN104492381A (en) | Heterogeneous TiO2/Co-metal organic framework (MOF) material as well as preparation method and application thereof | |
| CN101053821A (en) | Organic component supported charcoal chelating adsorbent and its preparation method and application | |
| CN100588620C (en) | Method for producing vectolite with waste and old lithium ion battery | |
| CN104927063A (en) | Method for adsorbing and recycling phenolic compounds in industrial wastewater and method for manufacturing adsorption materials | |
| CN107008230A (en) | Magnetic composite adsorbent and preparation method thereof | |
| CN110479204A (en) | A kind of high adsorption TiO2The application of the preparation method and its absorbing heavy metal ions in water of aeroge | |
| Al‐Hossainy et al. | Oxidation process and kinetics of bromothymol blue by alkaline permanganate | |
| CN104558598A (en) | One-step method for synthesizing poly(m-phenylenediamine) and graphene composite material and application of composite material to electric adsorption of heavy metal ions in water | |
| CN106362803A (en) | Ag-PANI embedded imprinting CdS/Fe3O4/C of Z-like heterojunction and preparation method of Ag-PANI embedded imprinting CdS/Fe3O4/C | |
| CN103769082B (en) | The charcoal load activity preparation method of MnOx, product and application | |
| CN103143237A (en) | Toluene-containing tail gas recycling process in refractory mica tape production | |
| CN100494081C (en) | Recovering handling method for amino C acid wastewater | |
| CN109908772A (en) | A kind of intercalation polymeric object lithium ion sieve/pvdf membrane and preparation method thereof | |
| CN105688795A (en) | Anionic dye adsorbent composite material as well as preparation method and application thereof | |
| CN107159094B (en) | The method of tetracycline in magnetic magnesium hydroxide adsorbent removal waste water | |
| CN103962107B (en) | A kind of preparation method of metal-modified humic acid defluorination absorbing material | |
| CN1193822C (en) | High-activity ferric oxide adsorbant and its prepn |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |