CN113233562A - Antibacterial flocculant containing quaternary phosphonium salt modified locust bean gum - Google Patents

Antibacterial flocculant containing quaternary phosphonium salt modified locust bean gum Download PDF

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CN113233562A
CN113233562A CN202110578863.7A CN202110578863A CN113233562A CN 113233562 A CN113233562 A CN 113233562A CN 202110578863 A CN202110578863 A CN 202110578863A CN 113233562 A CN113233562 A CN 113233562A
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locust bean
bean gum
phosphonium salt
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quaternary phosphonium
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林文浩
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Guangzhou Shangxin Purification Engineering Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/542—Phosphorus compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N57/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds
    • A01N57/34—Biocides, pest repellants or attractants, or plant growth regulators containing organic phosphorus compounds having phosphorus-to-halogen bonds; Phosphonium salts
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/283—Treatment of water, waste water, or sewage by sorption using coal, charred products, or inorganic mixtures containing them
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/50—Treatment of water, waste water, or sewage by addition or application of a germicide or by oligodynamic treatment
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
    • C02F1/54—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using organic material
    • C02F1/56—Macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00—Multistage treatment of water, waste water or sewage
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
    • C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
    • C08B37/006—Heteroglycans, i.e. polysaccharides having more than one sugar residue in the main chain in either alternating or less regular sequence; Gellans; Succinoglycans; Arabinogalactans; Tragacanth or gum tragacanth or traganth from Astragalus; Gum Karaya from Sterculia urens; Gum Ghatti from Anogeissus latifolia; Derivatives thereof
    • C08B37/0087—Glucomannans or galactomannans; Tara or tara gum, i.e. D-mannose and D-galactose units, e.g. from Cesalpinia spinosa; Tamarind gum, i.e. D-galactose, D-glucose and D-xylose units, e.g. from Tamarindus indica; Gum Arabic, i.e. L-arabinose, L-rhamnose, D-galactose and D-glucuronic acid units, e.g. from Acacia Senegal or Acacia Seyal; Derivatives thereof
    • C08B37/0093—Locust bean gum, i.e. carob bean gum, with (beta-1,4)-D-mannose units in the main chain branched with D-galactose units in (alpha-1,6), e.g. from the seeds of carob tree or Ceratonia siliqua; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00—Controlling or monitoring parameters in water treatment
    • C02F2209/11—Turbidity

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  • Life Sciences & Earth Sciences (AREA)
  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Molecular Biology (AREA)
  • Pest Control & Pesticides (AREA)
  • Botany (AREA)
  • Biochemistry (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Agronomy & Crop Science (AREA)
  • Emergency Medicine (AREA)
  • Plant Pathology (AREA)
  • Dentistry (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Separation Of Suspended Particles By Flocculating Agents (AREA)

Abstract

The invention relates to an antibacterial flocculant containing quaternary phosphonium salt modified locust bean gum, which consists of quaternary phosphonium salt modified locust bean gum, an auxiliary adsorption component, an auxiliary agent and a dispersing agent, wherein the quaternary phosphonium salt modified locust bean gum is prepared by oxidizing and ring-opening C2 and C3 positions on a natural locust bean gum galactomannan chain by using sodium periodate, and the obtained sodium carboxylate further performs ion exchange with the quaternary phosphonium salt; the prepared flocculant has good adsorption capacity and turbidity removal and antibacterial activity on organic matters in water, and can be used in water environment with serious pollution.

Description

Antibacterial flocculant containing quaternary phosphonium salt modified locust bean gum
Technical Field
The invention belongs to the technical field of water treatment, and particularly relates to an antibacterial flocculant containing a quaternary phosphonium salt modified locust bean gum.
Technical Field
The antibacterial flocculating agent is mainly concentrated on modification of quaternary ammonium salt cations, but the antibacterial duration is short, the medicinal dosage is large, however, with the use of a large amount of quaternary ammonium salt antibacterial agents, a plurality of bacteria and fungi gradually generate drug resistance to the quaternary ammonium salt antibacterial agents, and the antibacterial effect is gradually weakened. Compared with quaternary ammonium salts, quaternary phosphonium salts of the same family have stronger antibacterial performance, are easier to adsorb bacterial cells, are more stable than quaternary ammonium salts, do not react with general redox agents, acids, alkalis and the like, have wider pH application range and can exert better antibacterial activity, so that the modification of the quaternary phosphonium salts gradually becomes a hotspot of research in the field of antibacterial agents. On the other hand, as the research on biodegradable materials is more and more, natural or semi-synthetic substances such as cellulose and modified cellulose are mainly researched, but the flocculant has the defects of high crystallinity, poor biodegradability, difficult modification and the like, so that the development of the flocculant with good biodegradability, high antibacterial activity and good flocculation effect has wide application prospect.
Disclosure of Invention
In order to solve the above technical problems, the present invention provides a structure of a quaternary phosphonium salt modified locust bean gum and a method for preparing the same, and another object is to provide a method for preparing an antibacterial flocculant comprising a quaternary phosphonium salt modified locust bean gum and an effect of sewage treatment.
The flocculant consists of a quaternary phosphonium salt modified locust bean gum, an auxiliary adsorption component, an auxiliary agent and a dispersing agent;
the auxiliary adsorption component is one or a combination of activated carbon, bentonite and alumina;
the auxiliary agent is one or a combination of water-soluble starch, amylose and amylopectin;
the dispersant is one or a combination of methanol, ethanol, isopropanol, acetone and ethylene glycol dimethyl ether;
the structural formula of the quaternary phosphonium salt modified locust bean gum is shown as the following (I):
Figure BDA0003085450020000011
wherein R is
Figure BDA0003085450020000021
R1Is C6～12。
The preparation method of the antibacterial flocculating agent containing the phosphonium salt modified locust bean gum comprises the following steps:
1) oxidation reaction
Dissolving 0.1-1.0 g of natural locust bean gum in 30-80 mL of distilled water, adding 0.5-2.0 g of sodium periodate, reacting in a round-bottom flask, wrapping with tin foil paper to block light, avoiding the decomposition of the sodium periodate, and magnetically stirring at room temperature for 48 hours; adding ethylene glycol into the mixed solution, and stirring for 0.5-1.0 h to eliminate unreacted periodic acid to obtain locust bean oxide;
2) ion exchange reaction
Adding 0.5-2 g of locust bean gum oxide into 50-150 mL of quaternary phosphonium salt solution (0.08M), putting the mixture into a constant-temperature shaking incubator, carrying out ion exchange reaction at 120-160 rpm and a certain temperature, taking out a reactant after 2-12 h, washing the reactant with distilled water, and drying the reactant at 40 ℃ to constant weight to obtain quaternary phosphonium salt cation locust bean gum;
the total reaction scheme is shown as (II):
Figure BDA0003085450020000022
wherein R is
Figure BDA0003085450020000023
R1Is C6～12And X is halogen.
The quaternary phosphonium salt is one of hexyl triphenyl phosphonium bromide, octyl triphenyl phosphonium bromide and dodecyl triphenyl phosphonium bromide.
The preparation method of the antibacterial flocculating agent containing the phosphonium salt modified locust bean gum comprises the following steps:
dissolving 15-35 parts of quaternary phosphonium salt modified locust bean gum in 45-65 parts of dispersing agent, stirring for 0.5h at 30 ℃, adding 1-10 parts of auxiliary adsorption component and 1-10 parts of auxiliary agent, keeping the temperature of the substances at 40-50 ℃ in a nitrogen atmosphere, stirring and reacting for 2-4 h, heating to 50-80 ℃, reacting for 1-2 h, naturally cooling, and discharging;
preferably, the addition amount of the quaternary phosphonium salt modified locust bean gum is 30 parts, the dispersing agent is 50 parts of ethylene glycol dimethyl ether, the auxiliary adsorption component is 5 parts of activated carbon and 5 parts of alumina, and the auxiliary agent is 10 parts of amylopectin.
Compared with the prior art, the invention has the following beneficial effects:
(1) the flocculant of the invention has the highest sewage treatment effect and antibacterial activity by containing 30 parts (counted by hundreds) of PLBG-12;
(2) the antibacterial flocculant containing the phosphonium salt modified locust bean gum can reduce the content of organic matters in sewage to 18.8mg/L, has turbidity removal rate of over 90 percent and bacteriostasis rate of over 70 percent, wherein the inhibition rate of staphylococcus aureus can reach 100 percent.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the description is intended to be exemplary only, and is not intended to limit the scope of the present invention. Moreover, in the following description, descriptions of well-known structures and techniques are omitted so as to not unnecessarily obscure the concepts of the present invention.
Example 1
Respectively dissolving 30 parts of hexyl triphenyl phosphorus bromide modified locust bean gum (PLBG-6), octyl triphenyl phosphorus bromide modified locust bean gum (PLBG-8) and dodecyl triphenyl phosphorus bromide modified locust bean gum (PLBG-12) in 50 parts of ethylene glycol dimethyl ether, stirring for 0.5-1 h at 30 ℃, then adding 5 parts of active carbon, 5 parts of alumina and 10 parts of amylopectin, keeping the temperature of the substances at 40-50 ℃ under a nitrogen atmosphere, stirring for reacting for 2-4 h, then heating to 80 ℃ for reacting for 1-2 h, naturally cooling, and then discharging;
the three flocculants respectively containing PLBG-6, PLBG-8 and PLBG-12 are subjected to turbidity clearance (%), and COD(Cr)(mg/L) and the antibacterial ratio (%) were measured under the following conditions:
1) turbidity clearance (%): turbidity clearance calculation was performed according to equation (1),
Figure BDA0003085450020000031
2)COD(Cr)(mg/L): a COD determinator;
3) bacteriostatic rate (%): the antibacterial test conditions are determined according to a carrier soaking quantitative sterilization test method in WS/T650-2019, the test strains are escherichia coli, staphylococcus aureus and candida albicans, and the antibacterial rate X of the flocculant is determined to be as shown in formula (2):
Figure BDA0003085450020000032
in the formula: x is the bacteriostasis rate,%;
A0average colony number for control samples, CFU/plate;
A1the average colony count, CFU/plate, for the test samples;
the test method comprises the following steps: the test bacteria were washed 24h fresh slant cultures with PBS and diluted to about 5.0X 10 with PBS5CFU/mL～5.0×106CFU/mL, and preparing a bacterial suspension for later use. Taking a sterile test tube, firstly adding 5mL of sample, placing in a water bath at 20 +/-1 ℃ for 5min, then adding 0.1mL of test bacterial suspension, quickly mixing uniformly and immediately timing. When the interaction between the test bacteria and the sample is carried out for the specified time in the specification, 1.0mL of mixed solution of the test bacteria and the sample is respectively sucked and inoculated into 2 plates, and the culture medium is poured. When the bacterial count cannot be counted, performing 10-fold serial dilution by PBS, selecting appropriate dilution, respectively sucking 1.0mL of solution, inoculating 2 plates, and performing viable bacteria culture counting; all test samples and control samples are cultured at 36 +/-1 ℃, and bacterial propagules are cultured for 48h to observe results; and (5) culturing the candida albicans for 72 hours, observing the result, repeating the test for 3 times, and calculating the bacteriostasis rate.
And (4) judging a result: the bacteriostasis rate is more than or equal to 50-90 percent, and the bacteriostatic action is achieved; the bacteriostasis rate is more than or equal to 90 percent, and the antibacterial agent has stronger bacteriostasis.
The performances of three flocculants respectively containing PLBG-6, PLBG-8 and PLBG-12, which are measured according to the measuring method, are shown in Table 1;
table 1: performance measurement results of flocculants containing PLBG-6, PLBG-8 and PLBG-12
Figure BDA0003085450020000041
As can be seen from Table 1, the quaternary phosphonium salt flocculating agents containing three different alkane chain lengths have no obvious difference on the turbidity of sewage and the organic matter clearance rate, the turbidity clearance rate of three groups of flocculating agents can reach more than 90 percent, and the organic matter content is as low as 18.0mg/L, which shows that the flocculating agents have better sewage treatment effect; and as the length of the alkane chain is increased, the antibacterial activity of the flocculant is increased, wherein the flocculant containing PLBG-12 has the best antibacterial activity, the inhibition rate on staphylococcus aureus can reach 100 percent, and the length of the hydrophobic chain is reflected to be more destructive to cell walls and membranes of bacteria and fungi.
Example 2
Respectively dissolving 15-35 parts of PLBG-12 in 45-65 parts of ethylene glycol dimethyl ether with different contents, stirring for 0.5-1 h at 30 ℃, then adding 5 parts of activated carbon, 5 parts of alumina and 10 parts of amylopectin, keeping the temperature of the substances at 40-50 ℃ under a nitrogen atmosphere, stirring and reacting for 2-4 h, then heating to 80 ℃ for reacting for 1-2 h, naturally cooling and discharging;
wherein the content of each component in the flocculant is shown in table 2:
table 2 shows the contents of the respective components in the flocculants
Figure BDA0003085450020000051
According to the determination method in example 1, the turbidity clearance rate and COD of the sample of the flocculant in the five groups in the above example 2 are determined(Cr)And bacteriostatic rate, the results are shown in table 3;
table 3: performance test results with flocculant PLBG-12
Figure BDA0003085450020000052
The results in Table 2 show that the sewage treatment and antibacterial effects obtained by using the five groups of flocculant samples in Table 2 are different from each other in the content of PLBG-12, wherein the sewage treatment effect is best when the content of PLBG-12 is 30 parts by weight, organic matters can be as low as 18.0mg/L, the turbidity clearance rate reaches 91.6%, the bacterial antibacterial rate can reach more than 90%, the fungal antibacterial rate can reach more than 70%, and the fungal inhibition rate is better than that, wherein the gram-positive bacteria inhibition rate can reach 100%.
Blank group
Dissolving 30 parts of natural locust bean gum in 50 parts of glycol dimethyl ether, stirring for 0.5-1 h at 30 ℃, then adding 5 parts of activated carbon, 5 parts of alumina and 10 parts of amylopectin, keeping the temperature of the substances at 40-50 ℃ under a nitrogen atmosphere, stirring for reaction for 2-4 h, then heating to 80 ℃ for reaction for 1-2 h, naturally cooling, and discharging.
Comparing the example 2(2-4) with the blank group, the blank group has no antibacterial activity, and the turbidity removal rate and the organic matter removal capacity are 20-30% lower than those of the example 2(2-4), so that the quaternary phosphonium salt modified locust bean gum has good adsorption effect and antibacterial activity, greatly improves and enhances the physicochemical properties of the natural locust bean gum, widens the application of the natural locust bean gum only serving as a common thickening agent, has good biodegradability and does not cause burden to the ecological environment.

Claims (3)

1. An antibacterial flocculant containing a quaternary phosphonium salt modified locust bean gum is characterized by consisting of the quaternary phosphonium salt modified locust bean gum, an auxiliary adsorption component, an auxiliary agent and a dispersing agent;
the auxiliary adsorption component is one or a combination of activated carbon, bentonite and alumina;
the auxiliary agent is one or a combination of water-soluble starch, amylose and amylopectin;
the dispersant is one or a combination of methanol, ethanol, isopropanol, acetone and ethylene glycol dimethyl ether;
the structural formula of the quaternary phosphonium salt modified locust bean gum is shown as the following (I):
Figure FDA0003085450010000011
wherein R is
Figure FDA0003085450010000012
R1Is C6～12。
2. A preparation method of an antibacterial flocculating agent containing a phosphonium salt modified locust bean gum is characterized by comprising the following steps:
dissolving 15-35 parts of phosphonium salt modified locust bean gum in 45-65 parts of dispersing agent, stirring for 0.5-1 h at 30 ℃, adding 1-10 parts of auxiliary adsorption component and 1-10 parts of auxiliary agent, keeping the temperature of the substances at 40-50 ℃ in nitrogen atmosphere, stirring for reaction for 2-4 h, heating to 50-80 ℃, reacting for 1-2 h, naturally cooling, and discharging.
3. The method for preparing an antibacterial flocculant containing a quaternary phosphonium salt modified locust bean gum according to claim 2, wherein the quaternary phosphonium salt modified locust bean gum is added in an amount of 30 parts, the dispersing agent is 50 parts of ethylene glycol dimethyl ether, the auxiliary adsorption component is 5 parts of activated carbon and 5 parts of alumina, and the auxiliary agent is 10 parts of pullulan.
CN202110578863.7A 2021-05-26 2021-05-26 Antibacterial flocculant containing quaternary phosphonium salt modified locust bean gum Withdrawn CN113233562A (en)

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Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103709267A (en) * 2013-11-28 2014-04-09 江南大学 Preparation method of dialdehyde carboxymethyl chitosan

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103709267A (en) * 2013-11-28 2014-04-09 江南大学 Preparation method of dialdehyde carboxymethyl chitosan

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
王玉: "《药品检验（第1版）》", 31 October 2011, 中国医药科技出版社 *
贲长恩: "《组织化学（第1版）》", 30 November 2001, 人民卫生出版社 *

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Application publication date: 20210810