CN1896249A - Continuous catalytic synthesis of vitriol pyrite by solid microbion - Google Patents
Continuous catalytic synthesis of vitriol pyrite by solid microbion Download PDFInfo
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- CN1896249A CN1896249A CN 200610200611 CN200610200611A CN1896249A CN 1896249 A CN1896249 A CN 1896249A CN 200610200611 CN200610200611 CN 200610200611 CN 200610200611 A CN200610200611 A CN 200610200611A CN 1896249 A CN1896249 A CN 1896249A
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Abstract
A catalytic method for synthesizing ihleite continuously from fixed microbe is carried out by producing iron protoxide microbe into granular biological catalyst under acid condition by fixed technology, taking designed microbe inocuum as reactant, and catalytic synthesizing into high-purity ihleite pigment continuously under gentle condition in biological reactor. It's simple and efficient and can be used for continuous production.
Description
Technical Field
The invention relates to a method for continuously catalyzing and synthesizing jarosite by immobilized microorganisms.
Technical Field
Jarosite [ MFe]3(SO4)2(OH)6](M-K, Na or NH)4) Is a rare and expensive inorganic pigment with excellent performance, has the characteristics of strong covering power, good weather resistance, no toxicity and no acid resistance, and is particularly suitable for SO in the atmosphere2And acid rain, so that the paint has strong corrosion resistance, and iswidely applied to the art fields of painting and the like. The jarosite crystal content in the natural jarosite mineral is rare, and other impurities are often accompanied, so that the purification difficulty is high. Therefore, the technology for artificially synthesizing jarosite is widely researched and paid attention to.
In the prior art, firstly, ferric sulfate is reacted with alkaline compounds of potassium, sodium or ammonium at high temperature to obtain jarosite particles. However, the reaction product often contains ferric hydroxide colloid, so that the product has low purity, low yield and impure colorIs positive. Secondly, ferrous sulfate and K2SO4、K2CO3Or KOH is taken as a reactant and is stirred and reacted at high temperature under the action of a strong oxidant to obtain the catalyst. The reaction has the defects that the reaction needs heating equipment, the cost is high, and the energy consumption is large. Therefore, the conventional chemical synthesis method has the defects of harsh reaction conditions, complex process conditions, high cost, low product purity, low efficiency and the like, so that the application is limited to a certain extent.
In recent years, there have been studies to synthesize jarosite by microbiological methods. Chinese patent (03112950.1) discloses a method for synthesizing jarosite by microbial catalysis. It uses ferrous sulfate and one of potassium sulfate, sodium sulfate or ammonium sulfate as reactants and uses free microorganism Thiobacillus ferrooxidans LX5As a catalyst, jarosite is produced in batches at normal temperature.
The reaction equation for synthesizing the jarosite by the microbial catalysis is as follows:
wherein M is K, Na or NH4。
From this equation, it can be seen that there are several important drawbacks to this method: (1) the method can only carry out batch production, cannot carry out continuous operation and has low efficiency. (2) Before each batch of production, reactants are required to be added again, a large amount of microorganism cells which are subjected to enrichment culture and collection are inoculated again, the microorganism cannot grow and propagate in the reactor, and the microorganism is inconvenient to reuse, so that the operation process is complicated, and a large amount of microorganism cells and resources are wasted. (3) The effective cell concentration of the biocatalyst is insufficient. In general, the concentration of free cells in a liquid medium is only 108On the other hand, the low effective cell concentration limits the catalytic reaction rate. (4)Reaction conditions and environments need to be improved. Thiobacillus ferrooxidans can better maintain the high catalytic activity of cells at about 30 ℃ under the condition of a culture medium with proper proportion of C source, N source, energy source and inorganic salt. In this method, only sulfur is contained in the reactorFerrous acid and one of potassium sulfate, sodium sulfate or ammonium sulfate, and the reaction is only carried out at 25 ℃. These all limit the catalytic activity of the microorganisms to a large extent.
Disclosure of Invention
The invention aims to overcome the technical defects and provides a method for continuously catalytically synthesizing jarosite by using immobilized microorganisms.
The invention solves the technical problem by adopting the specific method steps that:
(1) theactivated and cultured high-efficiency microorganism immobilized particles are added into a reactor (the schematic diagram of the reactor is shown in figure 1), and the microorganism is a microorganism with ferrous ion oxidation capability under acidic conditions, and can be one of ferrous oxide thiobacillus, ferrous oxide leptospirillum or the mixture of the ferrous oxide thiobacillus, the ferrous oxide leptospirillum and the like. The method for immobilizing the microorganism is an embedding method, and among them, PVA freezing method and PVA-H are preferable3BO3The PVA-sulfate method and the patent (application No. 2005102003486, 2005102004915) in which the cell concentration in the immobilized particles is 109-1010one/mL is preferred.
(2) Feeding the designed reaction solution into the reactor at a dilution rate of 0.1-1.0, wherein the pH value of the reaction solution is 2.0-3.0, introducing air at 28-35 deg.C and normal pressure for reaction, and the aeration rate per 100mL of reactor is 30-250 mL/min. In the operation process, when the jarosite MFe3(SO4)2(OH)6When M is equal to K, the composition of the reaction solution is FeSO47H2O15-300g/L，K2SO41.5-30g/L，(NH4)2SO40.1-1.5g/L，KCl0.1g/L，K2HPO40.5g/L，MgSO47H2O0.5g/L，Ca(NO3)20.01g/L of, wherein Fe2+And K+The molar ratio of (A) to (B) is 3: 1; when M is Na, the composition of the reaction solution is FeSO47H2O15-300g/L，Na2SO41.4-28g/L，(NH4)2SO40.1-1.5g/L，NaCl0.1g/L，Na2HPO40.5g/L，MgSO47H2O0.5g/L，Ca(NO3)20.01g/L of, wherein Fe2+And Na+The molar ratio of (A) to (B) is 3: 1; m ═ NH4When the reaction solution is composed of FeSO47H2O15-300g/L，(NH4)2SO41.3-26g/L，NH4Cl0.1g/L，(NH4)2HPO40.5g/L，MgSO47H2O0.5g/L，Ca(NO3)20.01g/L of, wherein Fe2+And NH4 +In a molar ratio of 3: 1.
(3) Filtering and collecting the precipitate at the bottom of the reactor, washing with dilute sulfuric acid with pH value of 1.5-3.0, washing with distilled water, and naturally air drying or oven drying.
The invention has the beneficial effects that: because the immobilized microorganism particles are added into the reactor, reactants are redesigned and reaction conditions are controlled, the continuous and efficient catalytic synthesis of the jarosite is realized, the immobilized microorganism particles as a biocatalyst can be continuously and repeatedly used in the reactor, the microorganism catalytic activity is high, the operation process is simplified, the production efficiency is greatly improved, the product purity can reach more than 99 percent, and the large-scale industrial production and application of the biocatalytic synthesis are further promoted.
Fourth, detailed description of the invention
The first implementation example is as follows: (NH)4)Fe3(SO4)2(OH)6Preparation of
300mL of immobilized particles with higher biological activity (containing void volume) are added into a reactor with the effective reaction volume of 500mL, reaction liquid is introduced at the dilution rate of 0.2, and the composition of the reaction liquid is FeSO47H2O27.8g/L，(NH4)2SO41.8g/L，NH4Cl0.1g/L，(NH4)2HPO40.5g/L，MgSO47H2O0.5g/L，Ca(NO3)20.01g/L, the pH value of the reaction solution was 2.5, the reaction temperature was 31 ℃ under normal pressure, and the aeration rate was 650 mL/min. Collecting precipitate from the precipitation collector at the bottom of the reactor, and flushing with dilute sulfuric acid with pH of 1.5-3.0Washing with distilled water until the effluent is free of SO4 2-The product is naturally dried or dried below 80 ℃, and the yield of the primary reaction product is 95 percent calculated by Fe ions.
The analysis and identification of the product by X-ray and ICP-AES result is as follows:
XRD d-spacing(rel.intensity)：
5.79(38)，5.12(79)，3.66(11)，3.58(11)，3.10(100)，2.98(12)，2.90(18)，2.56(19)，1.95(14).
the content of ICP-AES elements is as follows: 35% Fe/%, 2.9% N/%, and 13.3% S/%, respectively
The results of the identification and (NH)4)Fe3(SO4)2(OH)6The standards were matched.
Example two was performed: KFe3(SO4)2(OH)6Preparation of
300mL of immobilized particles with higher biological activity (containing void volume) are added into a reactor with the effective reaction volume of 500mL, reaction liquid is introduced at the dilution rate of 0.3, and the composition of the reaction liquid is FeSO47H2O 83.4g/L，K2SO46.5g/L，(NH4)2SO40.1-1.5g/L，KCl0.1g/L，K2HPO40.5g/L，MgSO47H2O0.5g/L，Ca(NO3)20.01g/L, the pH value of the reaction solution was2.5, the reaction temperature was 31 ℃ under normal pressure, and the aeration rate was 850 mL/min. Collecting precipitate from a precipitate collector at the bottom of the reactor, washing with dilute sulfuric acid with pH of 1.5-3.0, and washing with distilled water until the effluent is free of SO4 2-The product is naturally dried or dried below 80 ℃, and the yield of the primary reaction product is 90 percent calculated by Fe ions.
The analysis and identification of the product by X-ray and ICP-AES result is as follows:
XRD d-spacing(rel.intensity)：
5.95(24)，5.68(14)，5.09(62)，3.67(27)，11(70)，3.08(100)，2.544(19)，2.275(29)，1.982(33)，1.833(35)，1.537(21).
the content of ICP-AES elements is as follows: 33.5% Fe/%, 7.7% K/%, and 12.7% S/%, respectively
Identification result and KFe3(SO4)2(OH)6The standards were matched.
Example three was performed: NaFe3(SO4)2(OH)6Preparation of
300mL of immobilized particles with higher biological activity (containing void volume) are added into a reactor with the effective reaction volume of 500mL, reaction liquid is introduced at the dilution rate of 0.4, and the composition of the reaction liquid is FeSO47H2O 55.6g/L，Na2SO44.4g/L，(NH4)2SO40.1-1.5g/L，NaCl0.1g/L，Na2HPO40.5g/L，MgSO47H2O0.5g/L，Ca(NO3)20.01g/L, the pH value of the reaction solution was 2.5, the reaction temperature was 31 ℃ under normal pressure, and the aeration rate was 450 mL/min. Collecting precipitate from a precipitate collector at the bottom of the reactor, washing with dilute sulfuric acid with pH of 1.5-3.0, and washing with distilled water until the effluent is free of SO4 2-The product is naturally dried or dried below 80 ℃, and the yield of the primary reaction product is 86 percent calculated by Fe ions.
The analysis and identification of the product by X-ray and ICP-AES result is as follows:
XRD d-spacing(rel.intensity)：
5.95(20)，5.59(29)，5.06(78)，3.12(90)，3.06(100)，2.54(19)，2.239(23)，1.979(25)，1.833(21).
the content of ICP-AES elements is as follows: fe/% -34.6%, Na/% -4.7%, S/% -13.1%
Identification results and NaFe3(SO4)2(OH)6The standards were matched.
Description of the drawings:
the attached figure is a schematic diagram of a reactor for continuously catalyzing and synthesizing the jarosite by the immobilized microorganisms.
Claims (4)
1. A method for continuously catalytically synthesizing jarosite by immobilized microorganisms is characterized in that the immobilized microorganisms are used as catalysts, culture solution is used as reactants, and the jarosite is continuously and efficiently catalytically synthesized.
2. The method of claim 1, wherein the microorganism used in the bioreactor is acidophilic iron oxidizing bacteria capable of converting Fe2+ into Fe3+, the acidophilic iron oxidizing bacteria can be any acidophilic microorganism or their mixture capable of oxidizing iron known to those skilled in the art of thiobacillus ferrooxidans, leptospirillum ferrooxidans, etc.
3. The method for continuously catalytically synthesizing jarosite by using immobilized efficient microorganisms according to claim 1, wherein the microorganism immobilization method is any one of embedding methods, preferably PVA freezing method, PVA-H3BO3 method, PVA-sulfate method and patent application No. 2005102003486, 2005102004915.
4. The method for the continuous catalytic synthesis of jarosite by the immobilized efficient microorganisms as claimed in claim 1, wherein the culture solution used as the reactant comprises: when the jarosite MFe3(SO4)2(OH)6 and M is equal to K, the composition of a reaction liquid is FeSO47H2O15-300g/L, K2SO41.5-3Og/L, (NH4)2SO40.1-1.5g/L, KCl0.1g/L, K2HPO40.5g/L, MgSO47H2O0.5g/L and Ca (NO3)20.01g/L, wherein the molar ratio of Fe2+ to K + is 3: 1; when M is Na, the composition of the reaction liquid is FeSO47H2O15-300g/L, Na2SO41.4-28g/L, (NH4)2SO40.1-1.5g/L, NaCl0.1g/L, Na2HPO40.5g/L, MgSO47H2O0.5g/L, Ca (NO3)20.01g/L, wherein the molar ratio of Fe2+ and Na + is 3: 1; when M is equal to NH4, the composition of the reaction liquid is FeSO47H2O15-300g/L, (NH4)2SO41.3-26g/L, NH4Cl0.1g/L, (NH4)2HPO40.5g/L, MgSO47H2O0.5g/L, Ca (NO3)20.01g/L, wherein the molar ratio of Fe2+ and NH4+ is 3: 1.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103740763A (en) * | 2014-01-20 | 2014-04-23 | 陈朋 | Method for preparing jarosite through microbial conversion |
| CN103818970A (en) * | 2014-03-06 | 2014-05-28 | 中国科学院成都生物研究所 | Synthesis method for nano yellow ferric oxide |
| CN103848459A (en) * | 2014-01-29 | 2014-06-11 | 浙江工业大学 | Method for preparing urchin-like alpha-Fe2O3 through biological mineralization |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1182248C (en) * | 2003-03-11 | 2004-12-29 | 南京农业大学 | Microbial-catalytic synthesizing method of pyrite ammonia alum |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103740763A (en) * | 2014-01-20 | 2014-04-23 | 陈朋 | Method for preparing jarosite through microbial conversion |
| CN103740763B (en) * | 2014-01-20 | 2015-09-30 | 陈朋 | The method of jarosite is prepared in a kind of microbial transformation |
| CN103848459A (en) * | 2014-01-29 | 2014-06-11 | 浙江工业大学 | Method for preparing urchin-like alpha-Fe2O3 through biological mineralization |
| CN103848459B (en) * | 2014-01-29 | 2015-08-26 | 浙江工业大学 | A kind of biomineralization legal system is for sea urchin shape α-Fe 2o 3method |
| CN103818970A (en) * | 2014-03-06 | 2014-05-28 | 中国科学院成都生物研究所 | Synthesis method for nano yellow ferric oxide |
| CN103818970B (en) * | 2014-03-06 | 2015-09-09 | 中国科学院成都生物研究所 | A kind of nanometer Zh 1 synthetic method |
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