CN109851813A - Sodium lignin sulfonate and the preparation method and application thereof containing more carboxyls and polyphosphonic acid base - Google Patents
Sodium lignin sulfonate and the preparation method and application thereof containing more carboxyls and polyphosphonic acid base Download PDFInfo
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Abstract
The invention discloses the sodium lignin sulfonate and the preparation method and application thereof containing more carboxyls and polyphosphonic acid base, the specific steps of the preparation method are as follows: a) adds water in glassed steel reaction vessels, hydrochloric acid and sulfuric acid is added after opening blender；B) HEDP, sodium lignin sulfonate, ammonium chloride, citric acid and zinc salt are continuously added；C) automatic heating control system is opened, when the temperature of charge in kettle is gradually increased to 80 DEG C, reflux condenser is opened, is slowly added into formaldehyde, is added in 1 hour；D) when reflux condenser starts reflux, temperature is maintained the reflux for, the reaction was continued 3~4 hours, and the sodium lignin sulfonate containing more carboxyls and polyphosphonic acid base is made.With the functional group oligomerisation of different chelations in the molecular structure of the compound, it is synergistic between different function group, with good exchange, dispersion and absorption property, dirt dispersion agent, anti-incrustation corrosion inhibitor and the prefilming agent in water treatment agent can be used as recirculating cooling water system.
Description
Technical field
The invention belongs to macromolecule chemical industry technical fields, and in particular to the sodium lignin sulfonate containing more carboxyls and polyphosphonic acid base
And preparation method thereof, also it is related to its application as anti-incrustation corrosion inhibitor in water treatment agent and pre- film in recirculating cooling water system.
Background technique
Sodium lignin sulfonate is a kind of byproduct of paper industry liquid waste processing recycling, more, the cheap, nothing with source
Poison, the advantages that being readily biodegradable are a kind of environmentally protective natural products.It is a kind of organic macromolecule, by phenylpropyl alcohol alkane knot
Structure unit is coupled by ehter bond and carbon-carbon bond, and molecular structure is more complicated, contains sulfonic group, phenolic hydroxyl group, methoxybenzene etc.
Chelation group and organic group are a kind of anionic surfactants, in water treatment agent, pesticide, printing and dyeing, cement and oil drilling
Equal fields are widely applied.As water treatment agent, sodium lignin sulfonate have certain scale inhibition and dispersion performance and corrosion inhibition, but by
The factors such as in source difference, molecular structure and performance inconsistency are bigger, and water solubility is poor, thus practical application is seldom.
Sodium lignin sulfonate contains many active function groups as described above, has preferable chemical reactivity, can be into
The series modified reactions such as row oxidation, ammonification, carboxy methylation, grafting and crosslinking further increase its chelating, exchange, dispersion and inhale
The performances such as attached, expand its application range.The study on the modification of sodium lignin sulfonate is become more and more active at present, researches and develops more performances
Better various derivatives, are a kind of inevitable development trends.
Patent CN101935255A, CN101941860A, CN102604120A carry out lignin using various oxidants
Oxidation modification prepares the dispersing agent with chelating ability.Patent CN101768280A is accessed short-chain fat polyamines using formaldehyde
Lignin, and using the reactivity of amino, carboxylic group is connected with chloroacetate reaction, so that it is multiple tooth to prepare both sexes lignin
Chelating resin.Chelating is made by the graft copolymerization acrylonitrile on bead lignin, further amidoximization in CN101357324A
Adsorption capacity is the chelating absorption resin of 5~15mmol/g.
The lignin derivative water solubility of above-mentioned modification is not high, and the application in fields such as water treatment agents is restricted.
CN104558633A to solve the above problems, improves the phenol of sodium lignin sulfonate using the method for microwave phenolate first
Then phosphonic acid base is introduced into its molecule using Mannich reaction principle by short-chain alkyl polyamines, is obtained water-soluble by hydroxy radical content
Good, the modified sodium lignosulfonate chelating agent containing phosphonic acid base that sequestering power increases substantially of property, promotes the product in Shui Chu
Manage the application in the fields such as agent.
CN104558633A provide the modified sodium lignosulfonate chelating agent containing phosphonic acid base preparation method the step of compared with
More, phenolic substances, epoxychloropropane and the short-chain alkyl polyamines used is all somewhat expensive, and the product phosphorus content of preparation is higher.Currently,
The development trend of water treatment agent is research and development and applies without phosphorus or low-phosphorous water treatment agent, to cope with the tight of phosphorus content in waste discharge
Lattice limitation.Modified sodium lignosulfonate chelating agent containing phosphonic acid base is as water treatment agent application, and common nothing currently on the market
Phosphorus organic polymer compares, and no matter does not all have apparent advantage in cost or in performance.
Summary of the invention
Present invention aim to address the above problem, cheap a kind of raw material, simple process, at low cost containing more carboxyls is provided
With the lignin sulfonic acid sodio-derivative of polyphosphonic acid base and the preparation method and application thereof.
To achieve the above object, the invention provides the following technical scheme:
The quality hundred of the preparation method of sodium lignin sulfonate containing more carboxyls and polyphosphonic acid base, various raw materials used is compared
Are as follows:
Sodium lignin sulfonate 5~10%
Sal-ammoniac 3~6%
Citric acid 0~25%
Zinc salt 0.5~1.2%
Hydroxy ethylene diphosphonic acid (HEDP) 5~45%
Water 10~40%
Hydrochloric acid 4~15%
Sulfuric acid 0.5~1.5%
Formalin 15~20%.
Further, the sodium lignin sulfonate is the grass using crop stalk to recycle in the pulping waste liquor of paper making raw material
Sodium lignin sulfonate is starched, or using wood waste as the wood pulp sodium lignin sulfonate that recycles in the pulping waste liquor of paper making raw material.
Further, the ammonium chloride is industrial grade ammonium chloride；Citric acid is technical grade citric acid.
Further, the zinc salt is white vitriol or anhydrous zinc chloride.
Further, the mass concentration of the hydroxy ethylene diphosphonic acid (HEDP) is 50~60%.
Further, the water is tap water or underground water.
Further, the hydrochloric acid is technical-grade hydrochloric acid, and mass concentration is greater than 31%；The sulfuric acid is technical grade sulfuric acid,
Mass concentration is greater than 92.5%.
Further, the mass concentration of the formalin is 37%.
The preparation method of the sodium lignin sulfonate containing more carboxyls and polyphosphonic acid base, comprising the following steps:
A) it adds water in glassed steel reaction vessels, opens the blender of reaction kettle, hydrochloric acid and sulfuric acid is then added, mixing is equal
It is even；
B) continue for HEDP, sodium lignin sulfonate, ammonium chloride, citric acid and zinc salt to be sequentially added in reaction kettle；
C) automatic heating control system for opening reaction kettle, the temperature of charge in reaction kettle is gradually risen；Work as reaction kettle
When interior temperature reaches 80 DEG C, the reflux condenser of reaction kettle is opened, starts to be slowly added into formaldehyde, is added in 1 hour；
D) when the reflux condenser of reaction kettle start reflux when, start timing, maintain the reflux for temperature, at reflux after
Continuous reaction 3~4 hours；After the reaction was completed, the sodium lignin sulfonate containing more carboxyls and polyphosphonic acid base is obtained.
In preparation step a), use tap water, technical hydrochloric acid, industrial sulphuric acid mixed solution as catalysis reaction medium；
In preparation step b), the zinc salt of addition is synthesis reaction catalyst.
The sodium lignin sulfonate containing more carboxyls and polyphosphonic acid base can be used as dirt dispersion agent, scale inhibition in water treatment agent
Corrosion inhibiter and prefilming agent are applied to recirculating cooling water system.
The beneficial effects of the present invention are:
Primary raw material used in the present invention is sodium lignin sulfonate, ammonium chloride, the citric acid of technical grade, hydroxy ethylene two
Phosphonic acids, source is wide, cheaply；With the simple process of original creation, single step reaction prepares the lignin containing polyhydroxy and polyphosphonic acid base
Sodium sulfonate；
The strong more carboxyls of chelating ability are introduced simultaneously in the molecule of the sodium lignin sulfonate containing polyhydroxy and polyphosphonic acid base
Citric acid-based and polyphosphonic acid base hydroxy ethylene diphosphonic acid base, add the original chelate group of sodium lignin sulfonate itself
Group, increases the density and synergistic effect of the various chelating functional groups in molecule, chelating, exchange, dispersion and the suction of the compound
It is attached etc. with better function.
It can be needed according to the practical use containing more carboxyls and the sodium lignin sulfonate of polyphosphonic acid base, in the matter of citric acid
Measuring charge ratio is 0~25% and in the range of the quality charge ratio of hydroxy ethylene diphosphonic acid is 5~45%, reduces hydroxyl Asia second
The dosage of base di 2 ethylhexyl phosphonic acid, equimolar increase the dosage of citric acid, and prepare a series of different phosphorus contents contains more carboxyls and more phosphines
The sodium lignin sulfonate of acidic group.The wherein low product of phosphorus content more meets the low-phosphorous or development without phosphatization of current water treatment agent and becomes
Gesture,
The present invention is independent or compounds with other organic and inorganic compounds, as the dirt dispersion agent in water treatment agent, resistance
Dirty corrosion inhibiter and prefilming agent are used for high concentration multiple, high calcium hardness, in the circulation of high chloride ion, anticorrosion-antiscaling property and
Pre-film effect is good.
Specific embodiment
By case study on implementation in detail below, the present invention is described in detail, but the scope of protection of present invention not office
It is limited to the range of case study on implementation statement.
Embodiment 1
42kg water is added in glassed steel reaction vessels, the blender of reaction kettle is opened, then sequentially adds hydrochloric acid 50kg, sulphur
Sour 7.8kg, HEDP172kg, wood pulp sodium lignin sulfonate 30kg, ammonium chloride 20kg and white vitriol 18kg.Open reaction kettle
Automatic heating system, the temperature of charge in reaction kettle is gradually risen, when the temperature in reaction kettle reaches 80 DEG C, is opened anti-
The reflux condenser for answering kettle starts to be slowly added into formaldehyde 76.4kg, add in 1 hour.When reflux condenser starts reflux,
Start timing, maintains the reflux for temperature, the reaction was continued at reflux 3 hours.After the reaction was completed, it is made and contains more carboxyls and more phosphines
The sodium lignin sulfonate of acidic group.
Embodiment 2
80kg water is added in glassed steel reaction vessels, the blender of reaction kettle is opened, then sequentially adds hydrochloric acid 20kg, sulphur
Sour 3.1kg, HEDP210.5kg, straw pulp sodium lignin sulfonate 30kg, ammonium chloride 20kg and white vitriol 18kg.Open reaction
The automatic heating system of kettle gradually rises the temperature of charge in reaction kettle, when the temperature in reaction kettle reaches 80 DEG C, opens
The reflux condenser of reaction kettle starts to be slowly added into formaldehyde 86.5kg, add in 1 hour.When reflux condenser starts to flow back
When, start timing, maintains the reflux for temperature, the reaction was continued at reflux 3 hours.After the reaction was completed, it is made and contains carboxyl and phosphine
The sodium lignin sulfonate of acidic group.
Embodiment 3
172kg water is added in glassed steel reaction vessels, the blender of reaction kettle is opened, then sequentially adds hydrochloric acid
33.4kg, sulfuric acid 5.2kg, HEDP52.7kg, citric acid 96.8kg, wood pulp sodium lignin sulfonate 30kg, ammonium chloride 20kg and seven
Water zinc sulphate 18kg.The automatic heating system for opening reaction kettle, the temperature of charge in reaction kettle is gradually risen, when in reaction kettle
Temperature when reaching 80 DEG C, open the reflux condenser of reaction kettle, start to be slowly added into formaldehyde 86.5kg, be added in 1 hour.
When reflux condenser starts reflux, starts timing, maintain the reflux for temperature, the reaction was continued at reflux 3 hours.It has reacted
The sodium lignin sulfonate containing more carboxyls and polyphosphonic acid base is made in Cheng Hou.
Embodiment 4
168kg water is added in glassed steel reaction vessels, the blender of reaction kettle is opened, then sequentially adds hydrochloric acid
37.6kg, sulfuric acid 5.9kg, HEDP34.3kg, citric acid 108kg, straw pulp sodium lignin sulfonate 30kg, ammonium chloride 20kg and seven
Water zinc sulphate 18kg.The automatic heating system for opening reaction kettle, the temperature of charge in reaction kettle is gradually risen, when in reaction kettle
Temperature when reaching 80 DEG C, open the reflux condenser of reaction kettle, start to be slowly added into formaldehyde 86.5kg, be added in 1 hour.
When reflux condenser starts reflux, starts timing, maintain the reflux for temperature, the reaction was continued at reflux 3 hours.It has reacted
The sodium lignin sulfonate containing more carboxyls and polyphosphonic acid base is made in Cheng Hou.
Embodiment 5
Contain Ca in 1000ml2+1440mg/L、Mg2296mg/L、Cl-The artificial preparation of 3308mg/L, total alkalinity 275mg/L
High rigidity and high chloride ion water sample in, be added containing embodiment 1 be made the sodium lignin sulfonate containing more carboxyls and polyphosphonic acid base
54%, polyether Quito amido tetramethylene phosphonic acid 22.8%, polyphosphonic acid base amino polyol 6.9%, phosphonic acid base threonine
6.3%, the compounding anti-incrustation corrosion inhibitor 20mg of anhydrous zinc chloride 6%, methyl-prop benzotriazole 4%, in 45 DEG C of water bath with thermostatic control
Pot according to the measurement-tosca method and GB/T18175-2014 water of GB/T16632-2008 water treatment agent scale-inhibiting properties at
The scale inhibition performance that the measurement rotary hanging plate method of reason agent corrosion inhibition measures is 93.2%, and the corrosion rate to carbon steel is 0.0058mm/
A, (professional standard 0.075mm//a), to the corrosion rate of stainless steel be 0.00mm/a (professional standard 0.004mm/a0, it is right
The corrosion rate of red copper alloy is 0.0016mm/a (professional standard 0.004mm/a).
Embodiment 6
Contain Ca in 1000ml2+250mg/L、Mg2296mg/L、Cl-437mg/L, total alkalinity 250mg/L are manually prepared
In the water sample of high rigidity and high chloride ion, it is added and the sodium lignin sulfonate containing more carboxyls and polyphosphonic acid base is made containing embodiment 2
59.8%, polyether Quito amido tetramethylene phosphonic acid 21.6%, polyphosphonic acid base amino polyol 6.6%, phosphonic acid base threonine
6.0%, the compounding anti-incrustation corrosion inhibitor 20mg of anhydrous zinc chloride 6%, according to GB/T16632- in 45 DEG C of thermostat water bath
The measurement of the measurement of 2008 water treatment agent scale-inhibiting properties-tosca method and GB/T18175-2014 water treatment agent corrosion inhibition
The scale inhibition performance that rotary hanging plate method measures is 95.3%, is 0.0mm/a to the corrosion rate of carbon steel, (professional standard be 0.075mm//
A), one layer of fluorescence uniform films blue are formed on the surface of carbon steel test piece.
Embodiment 7
Contain Ca in 1000ml2+1000mg/L、Mg2+0mg/L、Cl-2000mg/L, total alkalinity 320mg/L are manually prepared
In the water sample of high rigidity and high chloride ion, it is added and the sodium lignin sulfonate containing more carboxyls and polyphosphonic acid base is made containing embodiment 3
91.4%, anhydrous zinc chloride 6%, methyl-prop benzotriazole 2.6% compounding anti-incrustation corrosion inhibitor 40mg, in 45 DEG C of thermostatted water
According to the measurement-tosca method and GB/T18175-2014 water of GB/T16632-2008 water treatment agent scale-inhibiting properties in bath
The scale inhibition performance that the measurement rotary hanging plate method of inorganic agent corrosion inhibition measures is 97.2%, and the corrosion rate to carbon steel is
0.0058mm/a, (professional standard 0.075mm//a), the corrosion rate to stainless steel are that (professional standard is 0.00mm/a
0.004mm/a0, the corrosion rate to red copper alloy are 0.0016mm/a (professional standard 0.004mm/a).
Embodiment 8
Contain Ca in 1000ml2+250mg/L、Mg2+0mg/L、Cl-The height of 437mg/L, total alkalinity 250mg/L manually prepared
In the water sample of hardness and high chloride ion, be added containing embodiment 4 be made sodium lignin sulfonate 84% containing more carboxyls and polyphosphonic acid base,
The compounding anti-incrustation corrosion inhibitor 40mg of anhydrous zinc chloride 13%, methyl-prop benzotriazole 3%, is pressed in 45 DEG C of thermostat water bath
It is slow according to the measurement-tosca method and GB/T18175-2014 water treatment agent of GB/T16632-2008 water treatment agent scale-inhibiting properties
The scale inhibition performance that the measurement rotary hanging plate method of corrosion energy measures is 91.6%, and the corrosion rate to carbon steel is 0.0054mm/a, (industry
Standard is 0.075mm//a), the corrosion rate to stainless steel is that (professional standard 0.004mm/a0 closes red copper to 0.00mm/a
The corrosion rate of gold is 0.0016mm/a (professional standard 0.004mm/a).
Embodiment 9
In the commercially available pure water sample of 1000ml, it is added and the lignin containing more carboxyls and polyphosphonic acid base is made containing embodiment 4
Sodium sulfonate 81.4%, anhydrous zinc chloride 10%, methyl-prop benzotriazole 2.6% compounding anti-incrustation corrosion inhibitor 80mg, at 45 DEG C
Thermostat water bath in the scale inhibition performance that is measured according to the measurement rotary hanging plate method of GB/T18175-2014 water treatment agent corrosion inhibition
It is 91.6%, the corrosion rate to carbon steel is 0.028mm/a, (professional standard 0.075mm//a).This formula can be used as closed
Desalted water recirculating cooling water system.
Embodiment 10
Contain Ca in 1000ml2+1000mg/L、Mg2+0mg/L、Cl-2000mg/L, total alkalinity 320mg/L are manually prepared
In the water sample of high rigidity and high chloride ion, it is added and the sodium lignin sulfonate 87 containing more carboxyls and polyphosphonic acid base is made containing embodiment 4.
4%, anhydrous zinc chloride 10%, methyl-prop benzotriazole 2.6% compounding anti-incrustation corrosion inhibitor 40mg, in 45 DEG C of water bath with thermostatic control
Pot according to the measurement-tosca method and GB/T18175-2014 water of GB/T16632-2008 water treatment agent scale-inhibiting properties at
The scale inhibition performance that the measurement rotary hanging plate method of reason agent corrosion inhibition measures is 95.8%, and the corrosion rate to carbon steel is 0.0037mm/
A, (professional standard 0.075mm//a), to the corrosion rate of stainless steel be 0.00mm/a (professional standard 0.004mm/a0, it is right
The corrosion rate of red copper alloy is 0.00mm/a (professional standard 0.004mm/a).
The content not being described in detail in the present invention is the prior art.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Within mind and principle, any modification, equivalent replacement, improvement and so on be should all be included in the protection scope of the present invention.
Claims (11)
1. the preparation method of the sodium lignin sulfonate containing more carboxyls and polyphosphonic acid base, which comprises the following steps:
A) it adds water in glassed steel reaction vessels, opens the blender of reaction kettle, hydrochloric acid and sulfuric acid is then added, be uniformly mixed；
B) continue for hydroxy ethylene diphosphonic acid (HEDP), sodium lignin sulfonate, ammonium chloride, citric acid and zinc salt to be sequentially added instead
It answers in kettle；
C) automatic heating control system for opening reaction kettle, the temperature of charge in reaction kettle is gradually risen；When in reaction kettle
When temperature reaches 80 DEG C, the reflux condenser of reaction kettle is opened, starts to be slowly added into formaldehyde, is added in 1 hour；
D) when the reflux condenser of reaction kettle starts reflux, start timing, maintain the reflux for temperature, continue at reflux anti-
It answers 3~4 hours, after the reaction was completed, the lignin sulfonic acid sodio-derivative containing more carboxyls and polyphosphonic acid base is made.
2. the preparation method of the sodium lignin sulfonate according to claim 1 containing more carboxyls and polyphosphonic acid base, feature exist
In: it uses the mixed solution of tap water, technical hydrochloric acid, industrial sulphuric acid as catalysis reaction medium, the mass percent of dosage
It is followed successively by 10~40%, 4~15%, 0.5~1.5%.
3. the preparation method of the sodium lignin sulfonate according to claim 1 containing more carboxyls and polyphosphonic acid base, feature exist
In: its synthesis reaction catalyst used be industrial white vitriol or anhydrous zinc chloride, the mass percent number 0.5 of dosage~
1.2%.
4. the preparation method of the sodium lignin sulfonate according to claim 1 containing more carboxyls and polyphosphonic acid base, feature exist
The straw pulp lignin sulfonic acid recycled in the pulping waste liquor that: the sodium lignin sulfonate is using crop stalk as paper making raw material
Sodium or wood waste are the wood pulp sodium lignin sulfonate that recycles in the pulping waste liquor of paper making raw material, the mass percent of dosage
It is 5~10%.
5. the preparation method of the sodium lignin sulfonate according to claim 1 containing more carboxyls and polyphosphonic acid base, feature exist
In: the ammonium chloride is industrial grade ammonium chloride, and the mass percent of dosage is 3~6%.
6. the preparation method of the sodium lignin sulfonate according to claim 1 containing more carboxyls and polyphosphonic acid base, feature exist
In: the citric acid is technical grade citric acid, and the mass percent of dosage is 0~25%.
7. the preparation method of the sodium lignin sulfonate according to claim 1 containing more carboxyls and polyphosphonic acid base, feature exist
In: the mass concentration of the hydroxy ethylene diphosphonic acid is 50~60%, and the mass percent of dosage is 5~45%.
8. the preparation method of the sodium lignin sulfonate according to claim 1 containing more carboxyls and polyphosphonic acid base, feature exist
In: the mass concentration of the formalin is 37%, and the mass percent of dosage is 5~10%.
9. the preparation method of the sodium lignin sulfonate according to claim 1 containing more carboxyls and polyphosphonic acid base, feature exist
In: in the step c) plus the initial temperature of formaldehyde is 80 DEG C, and should be added in 60 minutes.
10. the preparation method of the sodium lignin sulfonate according to claim 1 containing more carboxyls and polyphosphonic acid base, feature exist
In: the reaction time in the step d) under reflux temperature and reflux state is 3~4 hours.
11. the preparation side of described in any item sodium lignin sulfonates containing more carboxyls and polyphosphonic acid base according to claim 1~10
Sodium lignin sulfonate obtained by method containing more carboxyls and polyphosphonic acid base, it is characterised in that: it can be used as the resistance in water treatment agent
Dirty dispersing agent, anti-incrustation corrosion inhibitor and prefilming agent are applied to recirculating cooling water system.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662462A (en) * | 2020-06-30 | 2020-09-15 | 金陵科技学院 | Preparation method of amination modified alkali lignin sodium phosphate oligomer cathode rust inhibitor |
| CN113893822A (en) * | 2021-10-22 | 2022-01-07 | 华南理工大学 | Lignin grading porous carbon with high specific surface area and preparation method and application thereof |
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| CN104558633A (en) * | 2015-01-08 | 2015-04-29 | 华南理工大学 | Modified sodium lignin sulfonate chelating agent containing phosphonic acid group and preparation method thereof |
| CN104710027A (en) * | 2013-12-13 | 2015-06-17 | 大连克林尔化学品科技有限公司 | Novel corrosion and scale inhibitor and production method thereof |
| CN105036372A (en) * | 2015-07-09 | 2015-11-11 | 潍坊友容实业有限公司 | Special scale inhibitor for saline-alkali soil moistube and preparation method for special scale inhibitor |
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- 2019-01-18 CN CN201910047085.1A patent/CN109851813A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104710027A (en) * | 2013-12-13 | 2015-06-17 | 大连克林尔化学品科技有限公司 | Novel corrosion and scale inhibitor and production method thereof |
| CN104558633A (en) * | 2015-01-08 | 2015-04-29 | 华南理工大学 | Modified sodium lignin sulfonate chelating agent containing phosphonic acid group and preparation method thereof |
| CN105036372A (en) * | 2015-07-09 | 2015-11-11 | 潍坊友容实业有限公司 | Special scale inhibitor for saline-alkali soil moistube and preparation method for special scale inhibitor |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111662462A (en) * | 2020-06-30 | 2020-09-15 | 金陵科技学院 | Preparation method of amination modified alkali lignin sodium phosphate oligomer cathode rust inhibitor |
| CN113893822A (en) * | 2021-10-22 | 2022-01-07 | 华南理工大学 | Lignin grading porous carbon with high specific surface area and preparation method and application thereof |
| CN113893822B (en) * | 2021-10-22 | 2022-08-09 | 华南理工大学 | Lignin grading porous carbon with high specific surface area and preparation method and application thereof |
| US11691121B2 (en) | 2021-10-22 | 2023-07-04 | South China University Of Technology | Lignin-based hierarchical porous carbon with high specific surface area and preparation method and application thereof |
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Application publication date: 20190607 |