CN111847444A - Method for removing calcium, magnesium and iron ions in phosphoric acid solution recycled in activated carbon preparation process - Google Patents
Method for removing calcium, magnesium and iron ions in phosphoric acid solution recycled in activated carbon preparation process Download PDFInfo
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- CN111847444A CN111847444A CN202010573136.7A CN202010573136A CN111847444A CN 111847444 A CN111847444 A CN 111847444A CN 202010573136 A CN202010573136 A CN 202010573136A CN 111847444 A CN111847444 A CN 111847444A
- Authority
- CN
- China
- Prior art keywords
- phosphoric acid
- magnesium
- organic acid
- activated carbon
- product
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 229910000147 aluminium phosphate Inorganic materials 0.000 title claims abstract description 46
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000000034 method Methods 0.000 title claims abstract description 27
- 229910052791 calcium Inorganic materials 0.000 title claims abstract description 22
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 22
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims description 24
- 239000011575 calcium Substances 0.000 title claims description 23
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 title claims description 21
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims description 21
- 239000011777 magnesium Substances 0.000 title claims description 21
- -1 iron ions Chemical class 0.000 title claims description 17
- 238000002360 preparation method Methods 0.000 title claims description 9
- 150000007524 organic acids Chemical class 0.000 claims abstract description 14
- 238000003825 pressing Methods 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract 2
- 239000011593 sulfur Substances 0.000 claims abstract 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 24
- 239000000047 product Substances 0.000 claims description 19
- 239000002244 precipitate Substances 0.000 claims description 11
- 235000006408 oxalic acid Nutrition 0.000 claims description 8
- 239000002366 mineral element Substances 0.000 claims description 4
- 239000012716 precipitator Substances 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 3
- 229910001576 calcium mineral Inorganic materials 0.000 claims 1
- 229910001608 iron mineral Inorganic materials 0.000 claims 1
- 229910001607 magnesium mineral Inorganic materials 0.000 claims 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 abstract description 12
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract description 9
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 230000008569 process Effects 0.000 abstract description 7
- 239000011347 resin Substances 0.000 abstract description 7
- 229920005989 resin Polymers 0.000 abstract description 7
- 150000002500 ions Chemical class 0.000 abstract description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract 1
- 125000004122 cyclic group Chemical group 0.000 abstract 1
- 238000007599 discharging Methods 0.000 abstract 1
- 229910052500 inorganic mineral Inorganic materials 0.000 abstract 1
- 239000011707 mineral Substances 0.000 abstract 1
- 238000011084 recovery Methods 0.000 abstract 1
- 230000000630 rising effect Effects 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 15
- 230000003213 activating effect Effects 0.000 description 7
- 238000004064 recycling Methods 0.000 description 7
- 239000007788 liquid Substances 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 230000004913 activation Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/318—Preparation characterised by the starting materials
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/30—Active carbon
- C01B32/312—Preparation
- C01B32/342—Preparation characterised by non-gaseous activating agents
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Removal Of Specific Substances (AREA)
Abstract
A method for removing Ca, Mg and Fe ions from phosphoric acid solution used in cyclic recovery of activated carbon includes such steps as choosing non-sulfur precipitant of Ca, Mg and Fe minerals to form insoluble deposit with very low solubility, filter pressing to separate and remove the deposit, and decomposing the organic acid Ad to CO or CO at 180 deg.C or lower2And H2O, the residual in the product is avoided, the ash content of the product is prevented from rising, the concentration of the organic acid is 50-70%, and the amount of the organic acid added into the recovered phosphoric acid is 3-5%. Sulfur dioxide polluting the environment cannot be generated in the production process, and the environment can be fully protected; the input amount is low, the price is relatively lower, the equipment investment is not needed, the input cost is low, and the investment of assets can be saved by 200 ten thousand yuan compared with the processing process of No. 001 resin; compared with sulfuric acid, no SO2Discharging and saving the tail gas treatment cost300 yuan/ton.
Description
Technical Field
The invention relates to a method for removing calcium, magnesium and iron ions in a phosphoric acid solution, in particular to a method for removing calcium, magnesium and iron ions in the phosphoric acid solution recycled in the preparation process of activated carbon.
Background
The phosphoric acid method activated carbon is widely applied to the market as a mainstream process in the field of wood activated carbon production. Phosphoric acid is used as an activating agent to produce activated carbon, and the phosphoric acid is used as the activating agent to be recycled in the production process, so that calcium, magnesium, iron and other ions in the recovered phosphoric acid liquid are continuously accumulated, the phosphoric acid liquid is aged and invalid, the effect of the phosphoric acid as the activating agent is seriously influenced, the quality of the product is seriously reduced, and the ash content of the product is increased.
To eliminate this effect, the prior art has two types; one is to use concentrated sulfuric acid to form precipitate with calcium, magnesium and iron ions in phosphoric acid to purify phosphoric acid and enhance the activating agent effect of phosphoric acid; the second method is to use No. 001 resin to carry out ion exchange to remove calcium, magnesium and iron ions in the phosphoric acid solution which is recycled.
However, both of the above-mentioned methods for recycling phosphoric acid after treatment have drawbacks. Firstly, the concentrated sulfuric acid method is used for treating phosphoric acid liquid for recycling, sulfuric acid and incomplete precipitated sulfate compounds remained in phosphoric acid after treatment are mixed in a phosphoric acid activating agent, a large amount of sulfur dioxide is discharged in an overproof manner at high temperature in the carbon activating process, and environmental pollution is caused. In addition, the 001 resin is used for treating the phosphoric acid liquid for recycling, calcium, magnesium and iron ions of the phosphoric acid are removed by ion exchange, a certain amount of high-salinity wastewater can be generated while the one-time equipment investment is large, and the method is not suitable for most activated carbon enterprises.
Disclosure of Invention
The technical problem to be solved is as follows: aiming at the problems in the prior art, the invention provides a method for removing calcium, magnesium and iron ions in a phosphoric acid solution recycled in the preparation process of activated carbon.
The technical scheme is as follows:
1. selecting sulfur-free precipitator containing mineral elements such as calcium, magnesium, iron and the like to form insoluble precipitate with small solubility product
（<Ca + (Cad)2-）=（Ca Ad ）=Ksp<1.0*10-7
The formed precipitate is removed by filter-pressing separation
2. The selected organic acid Ad is decomposed into CO and CO at the temperature of less than 180 DEG C2And H2O, can not remain in the product to avoid the rise of product ash content
3. The concentration of the organic acid is 50-70%, and the amount of the organic acid added into the recovered phosphoric acid is 3-5%.
The process route is as follows:
adding organic acid with the dissolving concentration of 50% -70%, adding 3-5% of Aa into the recovered phosphoric acid solution, stirring, standing for 15 hours, removing precipitates through filter pressing, treating the treated phosphoric acid solution, adding wood chips, stirring, and performing carbon activation to obtain a qualified product.
Has the advantages that:
1) sulfur dioxide polluting the environment cannot be generated in the production process, and the environment can be fully protected;
2) low input amountThe price is relatively lower, the equipment investment is not needed, the investment cost is low, and the investment of assets can be saved by 200 ten thousand yuan compared with the treatment process of No. 001 resin; compared with sulfuric acid, no SO 2The emission and the tail gas treatment cost are saved by 300 yuan/ton.
Detailed Description
The following detailed description of the embodiments of the disclosed method for removing calcium, magnesium and iron ions from recycled phosphoric acid is not intended to limit the scope of the invention.
Example 1
Through test and production inspection, the calcium, magnesium and iron ions in the phosphoric acid can be removed by adding oxalic acid solution into the circularly used phosphoric acid solution according to a proper proportion and stirring, precipitating and separating. In the laboratory stage, 0.5-1L of phosphoric acid recycling liquid is taken, 0.2-1g of oxalic acid mixture is added, flocculent particles appear immediately after the phosphoric acid recycling liquid is stirred, and precipitates are concentrated at the bottom after about 0.5 hour.
Specifically, about 1 cubic meter of phosphoric acid solution which is recycled is added with 0.5-5kg of oxalic acid mixed solution, 50kg-100kg of precipitate can appear through the stirring process, the treated phosphoric acid solution is used for production, the ash content of the produced activated carbon product is between 4% -6%, the iron salt content of the product is below 0.03%, the difference between the product quality and the product quality obtained through treatment by using sulfuric acid, resin and the like is almost zero, sulfur dioxide polluting the environment is not generated in the production process, and the treatment process is safe and convenient.
The method can well remove calcium, magnesium and iron ions in the phosphoric acid solution, and simultaneously the quality of the produced product can meet the requirement, the quality of the product cannot be reduced, and the treatment effect of using concentrated sulfuric acid and No. 001 resin can be achieved. The cost of treating 1 cubic meter of phosphoric acid solution recycled by oxalic acid is about 3-15 yuan; the cost of treating 1 cubic meter of phosphoric acid solution by using concentrated sulfuric acid for recycling is about 20-35 yuan; the cost of recycling phosphoric acid solution by treating 1 cubic meter with resin is about 100-300 yuan. Therefore, the phosphoric acid recycled by the oxalic acid method is suitable for most companies for producing the activated carbon by activating the phosphoric acid method.
The above description is only a preferred embodiment of the present invention, and the values and the range of values mentioned in the above description are not intended to limit the present invention, but only to provide a preferred embodiment of the present invention, and not to limit the present invention, and it is possible for those skilled in the art to make various modifications and variations. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (5)
1. A method for removing calcium, magnesium and iron ions in phosphoric acid solution recycled in the preparation process of activated carbon is characterized in that a sulfur-free calcium, magnesium and iron mineral element precipitator is selected to form insoluble precipitate with small solubility product, the formed precipitate is removed by filter pressing separation, and the selected organic acid Ad is decomposed into CO and CO at the temperature of less than 180 DEG C 2And H2O, the organic acid can not remain in the product to avoid the increase of the ash content of the product, the concentration of the organic acid is 50-70%, and the amount of the organic acid added into the recovered phosphoric acid is 3-5%.
2. The method for removing calcium, magnesium and iron ions in phosphoric acid solution recycled in the preparation process of activated carbon according to claim 1, which is characterized by comprising the following steps:
(1) selecting sulfur-free precipitator containing mineral elements such as calcium, magnesium, iron and the like to form insoluble precipitate with small solubility product
（<Ca + (Cad)2-）=（Ca Ad ）=Ksp<1.0*10-7
The formed precipitate is removed by filter pressing separation;
(2) the selected organic acid Ad decomposes CO and CO at a temperature of less than 180 DEG C2And H2O, no residue is left in the product to avoid the rise of product ash;
(3) the concentration of the organic acid is 50-70%, and the amount of the organic acid added into the recovered phosphoric acid is 3-5%.
3. The method for removing calcium, magnesium and iron ions in phosphoric acid solution recycled in activated carbon preparation process according to claim 1 or 2, wherein the non-sulfur organic acid precipitator capable of forming insoluble precipitate with low solubility product with mineral elements such as calcium, magnesium and iron is selected and includes but is not limited to oxalic acid.
4. The method for removing calcium, magnesium and iron ions in phosphoric acid solution recycled in activated carbon preparation process according to claim 1 or 2, characterized in that oxalic acid is used at a concentration of 50-70%.
5. The method for removing calcium, magnesium and iron ions in phosphoric acid solution recycled in the activated carbon preparation process according to claim 1 or 2, wherein the addition amount of oxalic acid used is 3-5%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010573136.7A CN111847444A (en) | 2020-06-22 | 2020-06-22 | Method for removing calcium, magnesium and iron ions in phosphoric acid solution recycled in activated carbon preparation process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010573136.7A CN111847444A (en) | 2020-06-22 | 2020-06-22 | Method for removing calcium, magnesium and iron ions in phosphoric acid solution recycled in activated carbon preparation process |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111847444A true CN111847444A (en) | 2020-10-30 |
Family
ID=72987116
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010573136.7A Pending CN111847444A (en) | 2020-06-22 | 2020-06-22 | Method for removing calcium, magnesium and iron ions in phosphoric acid solution recycled in activated carbon preparation process |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111847444A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102351161A (en) * | 2011-07-12 | 2012-02-15 | 浙江省林业科学研究院 | Method and device for reducing ash content of active carbon produced by phosphoric acid method |
| CN102838113A (en) * | 2012-08-31 | 2012-12-26 | 福建远翔化工有限公司 | Phosphoric acid impurity removal process in preparing activated carbon by phosphoric acid method |
| CN103648976A (en) * | 2011-06-23 | 2014-03-19 | 巴布科克诺尔有限公司 | Process and plant for decontaminating phosphoric acid solution |
| WO2016069263A1 (en) * | 2014-10-30 | 2016-05-06 | Jacobs Engineering Group Inc. | Method for removing iron in the manufacture of phosphoric acid |
| CN110759344A (en) * | 2019-11-29 | 2020-02-07 | 徐州天正活性炭厂 | Method for removing iron from phosphoric acid in production of activated carbon by phosphoric acid method |
-
2020
- 2020-06-22 CN CN202010573136.7A patent/CN111847444A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103648976A (en) * | 2011-06-23 | 2014-03-19 | 巴布科克诺尔有限公司 | Process and plant for decontaminating phosphoric acid solution |
| CN102351161A (en) * | 2011-07-12 | 2012-02-15 | 浙江省林业科学研究院 | Method and device for reducing ash content of active carbon produced by phosphoric acid method |
| CN102838113A (en) * | 2012-08-31 | 2012-12-26 | 福建远翔化工有限公司 | Phosphoric acid impurity removal process in preparing activated carbon by phosphoric acid method |
| WO2016069263A1 (en) * | 2014-10-30 | 2016-05-06 | Jacobs Engineering Group Inc. | Method for removing iron in the manufacture of phosphoric acid |
| CN110759344A (en) * | 2019-11-29 | 2020-02-07 | 徐州天正活性炭厂 | Method for removing iron from phosphoric acid in production of activated carbon by phosphoric acid method |
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| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201030 |