WO2013152492A1 - Method for adsorbing phenolic chemicals from water phase - Google Patents

Description

 Method for adsorbing phenolic organic matter in aqueous phase

 Technical field

 The present invention relates to the recovery of phenolic organics in the aqueous phase, and more particularly to the recovery of the aqueous phase by adsorption. Background technique

 The developed chemical industry, petrochemical industry, petroleum refining industry, coal carbonization industry, pesticide and pharmaceutical industry, etc., produce a large amount of wastewater containing phenolic organic matter, which seriously affects environmental safety. Due to the strong bactericidal function of phenolic organic substances, traditional microbial treatment methods are difficult to solve phenolic water pollution. The scientific and technical personnel in this field have carried out a lot of research and development work and developed many treatment methods. Among them, the flocculation method and the oxidation method are costly and produce secondary pollution, and do not have the attraction of commercial application; the membrane filtration method requires pretreatment of the sewage, and the film deformation often occurs. This method requires constant replacement of the new film and is also costly to process. Therefore, the most attractive treatment method recognized in the art is the adsorption method.

 Although the adsorption amount of activated carbon is high, the cost is high due to the serious loss during the regeneration process. Therefore, a variety of other substances have been studied for the adsorption of phenolic organics in aqueous phases, including fly ash, lignite, petroleum coke, rice hulls, clay, inorganic silicon, molecular sieves, jute fibers, sludge, almond shells, humans. Hair, rubber ends, sawdust, corn cobs, bamboo, palm fiber, pyrolysis animal bones, peat, used tea leaves, etc. However, the adsorption capacity of these substances is much different from that of activated carbon. In addition, polystyrene macroporous adsorption resins modified by covalent bond linking such as aniline, hydroxyl group, carbonyl group, cyano group, etc., can also be enhanced in adsorption capacity, but the modification method is costly.

 In summary, the art has found an adsorption method that can be simply regenerated, adsorbed in close proximity or better than activated carbon. Therefore, there is an urgent need in the art to develop an adsorption method which can be simply regenerated, adsorbed in a quantity close to or better than activated carbon. Summary of the invention

 A first object of the present invention is to obtain an adsorption method which can be simply regenerated, adsorbed in an amount close to or better than activated carbon.

A second object of the present invention is to obtain a macroporous adsorption resin modified by a lignin moiety for adsorbing a phenolic organic substance from an aqueous phase. A third object of the present invention is to obtain an application of a macroporous adsorption resin modified with a lignin fragment to adsorb a phenolic organic substance from an aqueous phase. A first aspect of the invention provides a method of adsorbing phenolic chemicals from an aqueous phase, providing a modified macroporous adsorption resin;

The macroporous adsorption resin modified by the lignin fragment adsorbs wastewater containing phenolic organic matter to obtain waste water having a reduced phenolic organic content. In a specific embodiment of the present invention, the adsorption capacity of the macroporous resin modified by the lignin fragment is a relative increase value of not less than 50%, and the relative increase value is a macroporous adsorption resin modified without a lignin fragment. The ability to adsorb phenol was determined as a standard. In a specific embodiment of the present invention, the macroporous resin modified by the lignin fragment is polystyrene (poly-divinyl benzene) or copolymerized with both. The (co-polymerization) high polymer is a skeleton macroporous adsorption resin. In a specific embodiment of the invention, the macroporous resin modified by the lignin fragment is neutral. In a specific embodiment of the present invention, the lignin fragment refers to a small molecule composed of 2 to 5 benzene rings obtained by hydrolysis of lignin. In a specific embodiment of the invention, the lignin fragments are used in an amount of from 5 to 10% by volume of the resin. In a specific embodiment of the present invention, wastewater containing phenolic organic matter is adsorbed by a column adsorption method. In a specific embodiment of the present invention, the aspect ratio is between 9:1 and 12:1. A second aspect of the present invention provides a macroporous adsorption resin modified by a lignin moiety for adsorbing a phenolic organic substance from an aqueous phase, the lignin fragment being a molecule obtained by hydrolysis of lignin by 2-5 a small molecule composed of benzene rings. A third aspect of the invention provides the use of the lignin fragment-modified macroporous adsorption resin for adsorbing phenolic organics from an aqueous phase.

detailed description

 The inventors have conducted extensive and intensive research to improve the preparation process, and the two aromatic aromatic compounds above the aromatic ring obtained by hydrolysis of lignin are used as modifiers and strengthening agents for strengthening the adsorption of phenol in the aqueous phase by macroporous adsorption resin. The ability of organic matter. The present invention has been completed on this basis. More specifically, it is. In the present invention, the term "contains" or "includes" means that the various ingredients can be used together in the mixture or composition of the present invention. Therefore, the terms "consisting essentially of . . . and consisting of " . . . are included in the terms "contains" or "includes". The various aspects of the invention are detailed below: Adsorption method

 A first aspect of the invention provides a method of adsorbing phenolic chemicals from an aqueous phase, comprising:

 Providing a modified macroporous adsorption resin modified with lignin fragments;

 The macroporous adsorption resin modified by the lignin fragment adsorbs wastewater containing phenolic organic matter to obtain wastewater having a reduced phenolic organic content. Wastewater containing phenolic organic matter

The invention can be applied to various waste waters containing phenolic organic substances. For example, the chemical industry, the petrochemical industry, the petroleum refining industry, the coal-carbonation industry, the pesticide and pharmaceutical industry, etc., which produce a large amount of wastewater containing phenolic organic matter. The phenolic substance referred to in the present invention means that all phenolic substances are suitable, and include a compound having a hydroxyl group on a single aromatic ring and a compound having a hydroxyl group on a condensed ring. Modified macroporous resin modified by lignin fragments

 The term "modification" refers to a method of increasing the adsorption capacity by first adsorbing a fragment of lignin, that is, by changing a resin structure by a non-covalent bond.

 The "macroporous adsorption resin" as used in the present invention means a neutral macroporous adsorption resin, poly-styrene and poly-divinyl benzene, or a mixture thereof (or The polymer of the copolymer is a macroporous adsorption resin having a skeleton, which does not have a cation or an anion, and prevents the resin from adsorbing the salt in the aqueous phase, so that the phenolic organic substance adsorbed has a good purity. The macroporous adsorption resin is commercially available.

 In a specific embodiment of the present invention, the macroporous resin modified by the lignin fragment is polystyrene (poly-divinyl benzene) or copolymerized with both. The (co-polymerization) high polymer is a skeleton macroporous adsorption resin.

 In a specific embodiment of the present invention, the adsorption capacity of the macroporous resin modified by the lignin fragment is a relative increase value of not less than 50%, and the relative increase value is a macroporous adsorption resin modified without a lignin fragment. The ability to adsorb phenol was determined as a standard. The "lignin fragment" as used in the present invention means a small molecule obtained after hydrolysis of lignin, and the molecule is composed of 2 to 5 benzene rings. More specifically, it refers to a small molecule containing 2 to 5 benzene rings separated by lignin alone hydrolyzate, or a fragment obtained by one-pot catalytic hydrolysis of lignin and cellulose. A small molecule composed of 2 to 5 benzene rings means a small molecule derived from a lignin raw material, all composed of a single aromatic ring (benzene ring) instead of a fused ring. The monophenyl ring small molecule obtained after the hydrolysis of lignin is itself a phenolic product, so it is not used to modify the macroporous adsorption resin; small molecules of 6 or more benzene rings will significantly reduce the flow rate of the liquid, and therefore, it is not preferable.

 The invention adopts a macroporous adsorption resin which can be directly purchased as a carrier, and uses a readily available lignin fragment as a modifying component to adsorb a certain amount of lignin fragments on the macroporous adsorption resin by non-covalent bond modification. The adsorption capacity of macroporous adsorption resin for phenol in aqueous phase.

The adsorption amount of the lignin fragment on the macroporous adsorption resin is preferably 5% to 10% (weight/volume ratio, that is, the ratio of the weight of the lignin fragment to the volume of the macroporous adsorption resin, g/liter, or kilogram/liter) . Less than 5%, The obtained modified macroporous adsorption resin has insufficient increase in the amount of adsorption of phenols in the aqueous phase, which is not preferable; and an amount exceeding 10% affects the flow rate of water on the column, which is also not preferable.

 The adsorption adopts a column type, and the height-to-diameter ratio is preferably between 9:1-12:1, which is less than the height-diameter ratio, and the adsorption is not complete, which is not preferable; above this height-diameter ratio, the amount of treatment per unit time is affected, so Not preferred.

 The technical scheme of the invention can greatly improve the adsorption capacity of the macroporous adsorption resin for phenol in the aqueous phase.

 The technical scheme of the invention can greatly improve the adsorption capacity of the macroporous adsorption resin for phenol in the aqueous phase.

 More specifically, the modified resin has an adsorption capacity higher than that of the unmodified resin by 50% or more, for example, if the unmodified resin has an adsorption capacity of 100 g of phenol/1 liter of resin, the modified resin is adsorbed. The capacity is equal to or higher than 150 phenols / 1 liter of resin. The following examples are given to better illustrate the invention, and are not intended to limit the invention to the following examples. Unless otherwise specified, the various starting materials of the present invention can be obtained commercially; or can be prepared according to conventional methods in the art. Unless otherwise defined or indicated, all of the professional and scientific terms used herein have the same meaning as those skilled in the art. Furthermore, any methods and materials similar or equivalent to those described may be employed in the methods of the invention. The above synthesis method is only a synthetic route of a part of the compounds of the present invention. According to the above examples, those skilled in the art can synthesize other compounds of the present invention by adjusting different methods, or the skilled person can synthesize the present invention according to the prior art. Compound. The synthesized compound can be further purified by column chromatography, high performance liquid chromatography or crystallization.

 Other aspects of the invention will be apparent to those skilled in the art from this disclosure.

 The invention is further illustrated below in conjunction with specific embodiments. It is to be understood that the examples are merely illustrative of the invention and are not intended to limit the scope of the invention. The experimental methods in the following examples which do not specify the specific conditions are usually determined in accordance with national standards. If there is no corresponding national standard, it is carried out in accordance with general international standards, general conditions, or in accordance with the conditions recommended by the manufacturer. Unless otherwise stated, all parts are by weight, all percentages are by weight, and the molecular weight of the polymer is number average molecular weight.

Unless otherwise defined or indicated, all of the professional and scientific terms used herein have the same meaning as those skilled in the art. Furthermore, any methods and materials similar or equivalent to those described may be employed in the methods of the invention. Example 1:

 Polystyrene macroporous resin DA201-C A total of 6 liters, soaked in 12 liters of alkaline brine (2% NaOH + 8% NaCl) for 12 hours, then washed with pure water until the pH is neutral. Load 6 1 liter columns with a 10:1 aspect ratio, Al, A2, Bl, B2, Cl, and C2.

 A lignin fragment of 420 g of hydrolyzed lignin was taken and dissolved in water to prepare an aqueous solution of about 5%, which was divided into 4 portions of 20%, 20%, 30%, and 30%, respectively. The two columns B1 and B2 respectively adsorb 20% of the solution, while C1 and C2 respectively adsorb 30% of the lignin fragment solution.

 The aqueous solution containing phenol having a pH of about 5 is a sample of 0.5 g/L, and is added to six adsorption columns of Al, A2, Bl, B2, Cl, and C2, and continuously detects the outlet velocity of the lower mouth and the effluent. The phenol concentration, when it reaches 0.5 g/L, is the adsorption saturation, and the total adsorption amount of the six adsorption columns is calculated.

 The results show that the macroporous adsorption resin modified with lignin fragments has a significantly increased ability to adsorb phenol. However, the flow rate of the outlet of the two adsorption columns of C1 and C2 is only 75% of the flow rate of B1 and B2, and the amount of adsorption is not increased much. Example 2:

In the first embodiment, six adsorption columns, such as Al, A2, Bl, B2, Cl, and C2, which are saturated, are regenerated with an aqueous solution of 8% NaOH, and washed to a pH of 12. The collected phenol product can be used, and then pure. The water was washed until the pH was neutral, and the procedure of Example 1 was repeated to obtain an adsorption amount of:

The results show that the adsorption method, the regeneration of the resin is very simple, and the phenolic product can be obtained. The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the technical scope of the present invention, the essence of the present invention. The technical content is broadly defined in the scope of the claims of the application, and any technical entity or method completed by others, if it is exactly the same as defined in the scope of the claims of the application, or an equivalent change, will be regarded as It is intended to be included within the scope of the claims. All documents mentioned in the present application are hereby incorporated by reference in their entirety in their entireties in the the the the the the the the In addition, it is to be understood that various modifications and changes may be made to the present invention, and the equivalents of the scope of the invention.

Claims

Rights request  A method of adsorbing a phenolic organic substance from an aqueous phase, characterized in that  Providing a macroporous adsorption resin modified with a lignin fragment;  The macroporous adsorption resin modified by the lignin fragment adsorbs wastewater containing phenolic organic matter to obtain wastewater having a reduced phenolic organic content. 2. The method according to claim 1, wherein the adsorption capacity of the macroporous resin modified by the lignin fragment is not less than 50%, and the relative increase is modified by the lignin-free fragment. The ability of the macroporous adsorption resin to adsorb phenol was determined as a standard. 3. The method according to claim 1, wherein the macroporous adsorption resin modified by the lignin fragment is composed of a polymer of polystyrene and polydivinylbenzene or a copolymer of the two. Macroporous adsorption resin. 4. The method according to claim 1, wherein the macroporous resin modified by the lignin fragment is neutral. The method according to claim 1, wherein the lignin fragment refers to a small molecule composed of 2 to 5 benzene rings obtained by hydrolyzing lignin. 6. The method according to claim 1, wherein the lignin fragment is used in an amount of 5 to 10% by volume of the resin.  7. The method according to claim 1, wherein the phenolic organic-containing wastewater is adsorbed by a column adsorption method. 8. The method according to claim 7, wherein the aspect ratio is between 9:1 and 12:1. 9. A macroporous adsorption resin modified by a lignin fragment for adsorbing a phenolic organic substance from an aqueous phase, characterized in that the lignin fragment means 2 to 5 molecules obtained after hydrolysis of lignin A small molecule composed of a benzene ring. A use of the lignin fragment-modified macroporous adsorption resin according to claim 9 for adsorbing a phenolic organic substance from an aqueous phase.