CN112758986B - Method for synthesizing Ca and Fe co-doped sodium vanadium bronze electrode material based on vanadium-rich liquid - Google Patents
Method for synthesizing Ca and Fe co-doped sodium vanadium bronze electrode material based on vanadium-rich liquid Download PDFInfo
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Abstract
The invention relates to a method for synthesizing a Ca and Fe co-doped sodium vanadium bronze electrode material based on a vanadium-rich solution. The technical scheme is as follows: adding oxalic acid dihydrate into the vanadium-rich liquid according to the molar ratio of oxalate ions to vanadium ions in the vanadium-rich liquid of (0.25-1) to 1, and stirring to obtain a solution I; adding sodium dodecyl benzene sulfonate into the solution I according to the molar ratio of vanadium ions to sodium dodecyl benzene sulfonate in the solution I of (50-800) to 1, and stirring to obtain a mixed solution II; and (3) placing the mixed solution II in a reaction kettle, reacting for 10-24 hours at 160-200 ℃, cooling to room temperature, and carrying out solid-liquid separation to obtain the Ca and Fe co-doped sodium vanadium bronze electrode material (hereinafter referred to as electrode material) based on the vanadium-rich solution. The electrode material synthesized by the invention is applied to an aqueous zinc ion battery, and the first charge-discharge capacity is 318-330 mAh/g under the current density of 0.2A/g. The invention has low synthesis cost, simple process and short synthesis period, and the synthesized electrode material has higher first charge-discharge capacity.
Description
Technical Field
The invention belongs to the technical field of synthesis of sodium vanadium bronze electrode materials. In particular to a method for synthesizing Ca and Fe co-doped sodium vanadium bronze electrode material based on vanadium-rich liquid.
Background
The sodium vanadium bronze can improve good supporting and conducting functions because sodium ions are positioned in the middle of the layered structure, is widely applied to secondary ion batteries such as lithium ion batteries, sodium ion batteries and zinc ion batteries, and is an electrochemical energy storage material with great potential.
At present, sodium vanadium bronzes are predominantly V2O5Sodium vanadate, ammonium polyvanadate and the like are used as raw materials and are synthesized by high-temperature solid-phase reaction, low-temperature chemical reaction or hydrothermal reaction.
' A tetragonal phase NaV2O5·H2O nano flaky powder, preparation method and application thereof (CN 108423711A) patent technology, naVO3And Na2S·9H2O is taken as a raw material, and hydrothermal reaction is carried out for 1 to 36 hours at the temperature of between 150 and 200 ℃ to synthesize NaV2O5·H2The O nanosheet powder is assembled into a lithium ion half-cell, the first charge-discharge capacity reaches 633mAh/g under the current density of 0.2A/g, and the capacity is 320mAh/g after 600 cycles of circulation. The method utilizes a one-step hydrothermal method to synthesize NaV2O5·H2The O nano sheet has higher first charge-discharge capacity when being applied to the lithium ion battery, but NaVO3And Na2S·9H2The price of O is higher, which is not beneficial to the actual industrialized production.
'A high-performance water system zinc ion battery anode material and a preparation method and application thereof' (CN 110474044A) patent technology, V2O5Sodium salt as raw material, regulating pH with acetic acid water solution, hydrothermal reacting at 90-200 deg.c for 12-72 hr to obtain NaV8O20·nH2O (n is 0.01-4) nanobelts, assembled into an aqueous zinc ion battery, and has the first charge-discharge capacity of 350mAh/g under the current density of 0.1A/g. The method utilizes NaV synthesized by a hydrothermal method8O20·nH2O (n is 0.01-4) nanobelt applied to zinc ion battery has higher first charge-discharge capacity, but raw material V2O5The price is high, and simultaneously, sodium salt and acetic acid are required to be added, so that the synthesis cost of the material is increased.
NaV preparation by shale vanadium extraction vanadium-rich liquid2O5The method (CN 108726570A) adopts the patent technology that oxalic acid or oxalate is added into vanadium-rich liquid obtained by extracting and back-extracting vanadium shale pickle liquor to be used as a reducing agent, and the hydrothermal reaction is carried out for 5 to 8 hours at the temperature of between 180 and 230 ℃ to obtain NaV2O5A micron rod. The method takes vanadium-rich liquid as raw material, and synthesizes NaV by a hydrothermal method2O5The price of the raw material of the micron rod is advantageous, but the material has higher Na content, lacks interlayer structure water and has unsatisfactory electrochemical performance.
Pan He, etc. (HE P, et al. Sodium Ion Stabilized sodium Oxide Nanowire Cathode for High-Performance Voltage to Ion Batteries [ J]Adv Energy Mater,2018,8 (10): 1702463.) with V2O5Dissolving in NaOH solution, adding PEG-4000, and hydrothermal reacting at 180 deg.CAfter 48 hours, na is obtained0.33V2O5Nanowires assembled as aqueous Zn/Na system0.33V2O5The first charge-discharge capacity of the battery is 367.1mAh/g under the current density of 0.1A/g. Na synthesized by the method0.33V2O5The nanowire is applied to the zinc ion battery, although the first charge-discharge capacity is higher, V needs to be firstly added2O5Alkali dissolution is carried out, PEG-4000 is added, and Na can be obtained through long-time hydrothermal reaction0.33V2O5The preparation process of the nano-wire has a long period.
Ping Gao et al (Ping Gao, et al. A Durable Na)0.56V2O5 Nanobelt Cathode Material Assisted by Hybrid Cationic Electrolyte for High～Performance Aqueous Zinc～Ion Batteries[J]ChemElectrochem,2020,7 (1).) at V2O5Powder and Na3C6H5O7·2H2O is taken as a raw material, and the hydrothermal reaction is carried out for 48 hours at the temperature of 160 ℃ to obtain Na0.56V2O5The nanobelt is applied to a water system zinc ion battery, the first charge-discharge capacity is 317mAh/g under the current density of 0.1A/g, and the technology adopts V with higher price2O5And Na3C6H5O7·2H2The synthesis time is longer because O is used as a raw material, and the prepared Na0.56V2O5The first charge-discharge capacity of the zinc ion battery applied by the nanobelt is not high.
Guo X et al (Guo X, fang G, zhang W, et al. Mechanical instruments of Zn)2+Storage in Sodium Vanadates[J]Advanced energy materials,2018,8 (27): 1801819.1-1801819.7.) with NH4VO3NaCl and sodium dodecyl sulfate as raw materials, performing hydrothermal reaction at 200 ℃ for 12 hours, calcining the obtained intermediate product at 400 ℃ in air atmosphere for 4 hours to obtain Na0.76V6O15The nanobelt is applied to a water-based zinc ion battery, and has the first charge-discharge capacity of 150mAh/g under the current density of 0.3A/g. The method is complex, needs two processes of hydrothermal reaction and high-temperature calcination, and simultaneously needs to addNaCl and sodium dodecyl sulfate, na obtained0.76V6O15The application of the nanobelt to the first charge-discharge capacity of the zinc ion battery is not ideal.
In summary, the existing preparation method of the sodium-vanadium bronze electrode material has the technical defects that: a large amount of sodium salt needs to be added, the synthesis cost is high, the synthesis process is complex, the synthesis period is long, and the obtained sodium vanadium bronze electrode material has low first charge-discharge capacity.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a method for synthesizing a Ca and Fe co-doped sodium vanadium bronze electrode material based on a vanadium-rich liquid, which has the advantages of low synthesis cost, simple process and short synthesis period.
In order to achieve the purpose, the technical scheme adopted by the invention comprises the following specific steps:
step one, adding oxalic acid dihydrate into the vanadium-rich liquid according to the molar ratio of oxalate ions to vanadium ions in the vanadium-rich liquid of (0.25-1) to 1, and stirring for 1-3 hours to obtain a solution I.
And step two, adding the sodium dodecyl benzene sulfonate into the solution I according to the molar ratio of the vanadium ions to the sodium dodecyl benzene sulfonate in the solution I of (50-800) to 1, and stirring for 0.5-1 hour to obtain a mixed solution II.
And step three, placing the mixed solution II in a reaction kettle, reacting for 10-24 hours at 160-200 ℃, cooling to room temperature, and carrying out solid-liquid separation to obtain the Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich solution.
The vanadium-rich liquid is a product purified and enriched in wet extraction, purification and enrichment, ammonium salt vanadium precipitation and high-temperature calcination of a vanadium-containing substance; the vanadium-rich liquid: the concentration of vanadium is 5-50 g/L, the concentration of Na is 5-200 g/L, the concentration of Ca is 0.05-10 g/L, the concentration of Fe is 0.05-10 g/L, the concentration of Al is less than or equal to 0.05g/L, the concentration of P is less than or equal to 0.05g/L, and the concentration of Si is less than or equal to 0.05g/L; the pH value is 1-4, and the content of pentavalent vanadium in the total vanadium is more than 90wt%.
The purity of the oxalic acid dihydrate is industrial grade.
The purity of the sodium dodecyl benzene sulfonate is industrial grade.
Due to the adoption of the technical scheme, compared with the prior art, the invention has the following positive effects:
the vanadium-rich liquid adopted by the invention is a product purified and enriched in wet extraction-purification and enrichment-ammonium salt vanadium precipitation-high temperature calcination of vanadium-containing substances; the vanadium-rich liquid is rich in vanadium and sodium elements, and the content of other impurity elements is low, so that the vanadium-rich liquid can be used as a hydrothermal reaction raw material to replace expensive industrial products such as ammonium metavanadate, vanadium pentoxide or sodium metavanadate, and sodium salt does not need to be additionally added, so that the synthesis cost is remarkably reduced.
The invention directly starts from a vanadium-rich liquid, takes oxalic acid dihydrate as a reducing agent, takes sodium dodecyl benzene sulfonate as a surfactant, and carries out hydrothermal reaction for 10-24 hours at 160-200 ℃ to synthesize the micron-sized Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich liquid. The method does not need to dissolve the vanadium-containing raw material and does not need a high-temperature calcination process, so that the synthesis period is obviously shortened and the synthesis process is simpler.
The Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich liquid is synthesized by taking the vanadium-rich liquid as a raw material through a simple one-step hydrothermal method, is applied to a zinc ion battery, and has the first charge-discharge capacity of 318-330 mAh/g under the current density of 0.2A/g.
According to the invention, the vanadium-rich liquid with low price is used as a raw material, sodium salt is not required to be additionally added, and the Ca and Fe co-doped sodium vanadium bronze electrode material with high first charge-discharge capacity based on the vanadium-rich liquid is synthesized by a simple one-step hydrothermal method.
Therefore, the method has the characteristics of low synthesis cost, simple process and short synthesis period, and the synthesized Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich liquid has higher first charge-discharge capacity.
Drawings
FIG. 1 is an X-ray diffraction spectrum of a Ca and Fe co-doped sodium vanadium bronze electrode material based on a vanadium-rich liquid;
FIG. 2 is a scanning electron microscope image of the Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich liquid shown in FIG. 1;
FIG. 3 is a first charging and discharging curve of the Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich liquid shown in FIG. 1.
Detailed Description
The invention is further described with reference to the following figures and detailed description, without limiting its scope.
A method for synthesizing Ca and Fe co-doped sodium vanadium bronze electrode material based on vanadium-rich liquid. The synthesis method of the present embodiment comprises the steps of:
step one, adding oxalic acid dihydrate into the vanadium-rich liquid according to the molar ratio of oxalate ions to vanadium ions in the vanadium-rich liquid of (0.25-1) to 1, and stirring for 1-3 hours to obtain a solution I.
And step two, adding the sodium dodecyl benzene sulfonate into the solution I according to the molar ratio of the vanadium ions to the sodium dodecyl benzene sulfonate in the solution I of (50-800) to 1, and stirring for 0.5-1 hour to obtain a mixed solution II.
And step three, placing the mixed solution II in a reaction kettle, reacting for 10-24 hours at 160-200 ℃, cooling to room temperature, and carrying out solid-liquid separation to obtain the Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich solution.
The vanadium-rich liquid: the concentration of vanadium is 5-50 g/L, the concentration of Na is 5-200 g/L, the concentration of Ca is 0.05-10 g/L, the concentration of Fe is 0.05-10 g/L, the concentration of Al is less than or equal to 0.05g/L, the concentration of P is less than or equal to 0.05g/L, and the concentration of Si is less than or equal to 0.05g/L; the pH value is 1-4, and the content of pentavalent vanadium in the total vanadium is more than 90wt%.
In this embodiment:
the vanadium-rich liquid is a product purified and enriched in wet extraction, purification and enrichment, ammonium salt vanadium precipitation and high-temperature calcination of a vanadium-containing substance;
the purity of the oxalic acid dihydrate is in industrial grade;
the purity of the sodium dodecyl benzene sulfonate is industrial grade.
The details in the embodiments are not repeated.
Example 1
A method for synthesizing Ca and Fe co-doped sodium vanadium bronze electrode material based on vanadium-rich liquid. The synthesis method of the present embodiment comprises the steps of:
step one, adding oxalic acid dihydrate into the vanadium-rich liquid according to the molar ratio of oxalate ions to vanadium ions in the vanadium-rich liquid of 0.25: 1, and stirring for 1 hour to obtain a solution I.
And step two, adding the sodium dodecyl benzene sulfonate into the solution I according to the molar ratio of the vanadium ions to the sodium dodecyl benzene sulfonate in the solution I being 50: 1, and stirring for 0.5 hour to obtain a mixed solution II.
And step three, placing the mixed solution II in a reaction kettle, reacting for 10 hours at 160 ℃, cooling to room temperature, and carrying out solid-liquid separation to obtain the Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich solution.
The vanadium-rich liquid: the vanadium concentration is 5.05g/L, the Na concentration is 5.2g/L, the Ca concentration is 0.051/L, the Fe concentration is 0.052g/L, the Al concentration is less than or equal to 0.05g/L, the P concentration is 0.01g/L, and the Si concentration is 0.01g/L; the pH was 1 and the pentavalent vanadium content of the total vanadium was 90.05wt%.
The Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich solution, which is synthesized by the invention, is applied to a water-based zinc ion battery, and the first charge-discharge capacity is 318mAh/g under the current density of 0.2A/g.
Example 2
A method for synthesizing Ca and Fe co-doped sodium vanadium bronze electrode material based on vanadium-rich liquid. The synthesis method of the present embodiment comprises the steps of:
step one, adding oxalic acid dihydrate into the vanadium-rich liquid according to the molar ratio of oxalate ions to vanadium ions in the vanadium-rich liquid of 0.5: 1, and stirring for 1.5 hours to obtain a solution I.
And step two, adding the sodium dodecyl benzene sulfonate into the solution I according to the molar ratio of the vanadium ions to the sodium dodecyl benzene sulfonate in the solution I being 200: 1, and stirring for 0.7 hour to obtain a mixed solution II.
And step three, placing the mixed solution II in a reaction kettle, reacting for 24 hours at 170 ℃, cooling to room temperature, and carrying out solid-liquid separation to obtain the Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich liquid.
The vanadium-rich liquid: the vanadium concentration is 25.05g/L, the Na concentration is 100.05g/L, the Ca concentration is 5.5g/L, the Fe concentration is 6.5g/L, the Al concentration is 0.02g/L, the P concentration is 0.04g/L, and the Si concentration is 0.02g/L; the pH was 2 and the pentavalent vanadium content of the total vanadium was 91wt%.
The Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich liquid, which is synthesized by the invention, is applied to a water-based zinc ion battery, and the first charge-discharge capacity is 327mAh/g under the current density of 0.2A/g.
Example 3
A method for synthesizing a Ca and Fe co-doped sodium vanadium bronze electrode material based on vanadium-rich liquid. The synthesis method of the present embodiment comprises the steps of:
step one, adding oxalic acid dihydrate into the vanadium-rich liquid according to the molar ratio of oxalate ions to vanadium ions in the vanadium-rich liquid of 0.75: 1, and stirring for 2.5 hours to obtain a solution I.
And step two, adding the sodium dodecyl benzene sulfonate into the solution I according to the molar ratio of the vanadium ions to the sodium dodecyl benzene sulfonate in the solution I being 400: 1, and stirring for 0.9 hour to obtain a mixed solution II.
And step three, placing the mixed solution II in a reaction kettle, reacting for 18 hours at 180 ℃, cooling to room temperature, and carrying out solid-liquid separation to obtain the Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich solution.
The vanadium-rich liquid: the vanadium concentration is 35.55g/L, the Na concentration is 150.45g/L, the Ca concentration is 8.5g/L, the Fe concentration is 7.5g/L, the Al concentration is 0.04g/L, the P concentration is 0.04g/L, and the Si concentration is 0.03g/L; the pH was 3 and the pentavalent vanadium content of the total vanadium was 93wt%.
The Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich liquid, which is synthesized by the invention, is applied to a water-based zinc ion battery, and the first charge-discharge capacity is 322mAh/g under the current density of 0.2A/g.
Example 4
A method for synthesizing a Ca and Fe co-doped sodium vanadium bronze electrode material based on vanadium-rich liquid. The synthesis method of the present embodiment comprises the steps of:
step one, adding oxalic acid dihydrate into the vanadium-rich liquid according to the molar ratio of oxalate ions to vanadium ions in the vanadium-rich liquid of 1: 1, and stirring for 3 hours to obtain a solution I.
And step two, adding the sodium dodecyl benzene sulfonate into the solution I according to the molar ratio of the vanadium ions to the sodium dodecyl benzene sulfonate in the solution I of 800: 1, and stirring for 1 hour to obtain a mixed solution II.
And step three, placing the mixed solution II in a reaction kettle, reacting for 24 hours at the temperature of 200 ℃, cooling to room temperature, and carrying out solid-liquid separation to obtain the Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich solution.
The vanadium-rich liquid: the vanadium concentration is 49.85g/L, the Na concentration is 199.75g/L, the Ca concentration is 9.95g/L, the Fe concentration is 9.93g/L, the Al concentration is 0.05g/L, the P concentration is 0.05g/L, and the Si concentration is 0.05g/L; the pH was 4 and the pentavalent vanadium content of the total vanadium was 95wt%.
The Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich liquid, which is synthesized by the invention, is applied to a water-based zinc ion battery, and the first charge-discharge capacity is 330mAh/g under the current density of 0.2A/g.
Compared with the prior art, the specific implementation mode has the following positive effects:
the vanadium-rich liquid adopted by the specific embodiment is a product purified and enriched in the processes of wet extraction, purification and enrichment, ammonium salt vanadium precipitation and high-temperature calcination of vanadium-containing substances; the vanadium-rich liquid is rich in vanadium and sodium elements, has low content of other impurity elements, can be used as a hydrothermal reaction raw material to replace expensive industrial products such as ammonium metavanadate, vanadium pentoxide or sodium metavanadate, and does not need to add sodium salt additionally, so that the synthesis cost is obviously reduced.
The specific embodiment directly starts from a vanadium-rich liquid, oxalic acid dihydrate or oxalic acid is used as a reducing agent, sodium dodecyl benzene sulfonate is used as a surfactant, and the hydrothermal reaction is carried out for 10 to 24 hours at the temperature of 160 to 200 ℃ to synthesize the micron-sized Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich liquid. The method does not need to dissolve the vanadium-containing raw material and does not need a high-temperature calcination process, so that the synthesis period is obviously shortened and the synthesis process is simpler.
The specific embodiment takes the vanadium-rich liquid as a raw material, and the Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich liquid is synthesized by a simple one-step hydrothermal method, is applied to a zinc ion battery, and has the initial charge-discharge capacity of 318-330 mAh/g at the current density of 0.2A/g.
The Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich liquid synthesized by the specific embodiment is shown in the attached drawing: FIG. 1 is an X-ray diffraction pattern of Ca and Fe co-doped sodium vanadium bronze electrode material based on vanadium-rich liquid synthesized in example 4; FIG. 2 is a scanning electron microscope image of the Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich liquid shown in FIG. 1; FIG. 3 is a first charge-discharge curve of the Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich liquid shown in FIG. 1. As can be seen from fig. 1: the synthesized Ca and Fe co-doped sodium vanadium bronze electrode material based on vanadium-rich liquid and Na0.7Ca0.3(V7.6Fe0.4)O20·4H2The X-ray diffraction peaks of O (PDF No. 85-1407) corresponded to each other, and had a similar crystal structure. As can be seen from fig. 2: the synthesized Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich liquid is granularity<20um of microparticles; as can be seen from fig. 3: the first charge-discharge capacity of the synthesized Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich liquid is 330mAh/g at the current density of 0.2A/g. The Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich liquid shown in FIG. 1 is subjected to ICP elemental analysis: the V concentration was 817.8ppm, the Na concentration was 106.356ppm, the Ca concentration was 0.807ppm, and the Fe concentration was 1.479ppm.
According to the specific embodiment, the vanadium-rich liquid with low price is used as a raw material, sodium salt does not need to be additionally added, and the Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich liquid with high initial charge-discharge capacity is synthesized through a simple one-step hydrothermal method.
Therefore, the specific embodiment has the characteristics of low synthesis cost, simple process and short synthesis period, and the synthesized Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich liquid has higher first charge-discharge capacity.
Claims (3)
1. A method for synthesizing Ca and Fe co-doped sodium vanadium bronze electrode material based on vanadium-rich liquid is characterized by comprising the following specific steps:
adding oxalic acid dihydrate into the vanadium-rich liquid according to the molar ratio of oxalate ions to vanadium ions in the vanadium-rich liquid of (0.25-1) to 1, and stirring for 1-3 hours to obtain a solution I;
step two, adding the sodium dodecyl benzene sulfonate into the solution I according to the molar ratio of vanadium ions to the sodium dodecyl benzene sulfonate in the solution I of (50-800) to 1, and stirring for 0.5-1 hour to obtain a mixed solution II;
step three, placing the mixed solution II in a reaction kettle, reacting for 10-24 hours at 160-200 ℃, cooling to room temperature, and carrying out solid-liquid separation to obtain a Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich solution;
the vanadium-rich liquid is a product purified and enriched in wet extraction-purification and enrichment-ammonium salt vanadium precipitation-high-temperature calcination of vanadium-containing substances; the vanadium-rich liquid: the concentration of vanadium is 5-50 g/L, the concentration of Na is 5-200 g/L, the concentration of Ca is 0.05-10 g/L, the concentration of Fe is 0.05-10 g/L, the concentration of Al is less than or equal to 0.05g/L, the concentration of P is less than or equal to 0.05g/L, and the concentration of Si is less than or equal to 0.05g/L; the pH value is 1-4, and the content of pentavalent vanadium in the total vanadium is more than 90wt%.
2. The method for synthesizing the Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich liquid according to claim 1, wherein the purity of the oxalic acid dihydrate is industrial grade.
3. The method for synthesizing the Ca and Fe co-doped sodium vanadium bronze electrode material based on the vanadium-rich liquid according to claim 1, wherein the purity of the sodium dodecyl benzene sulfonate is industrial grade.
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