CN107115841A - Multistage pickling aftertreatment technology prepares ultralow ash content plant base charcoal - Google Patents
Multistage pickling aftertreatment technology prepares ultralow ash content plant base charcoal Download PDFInfo
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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Abstract
Ultralow ash content plant base charcoal technique is prepared the invention discloses a kind of multistage pickling post processing.The technical scheme is that under normal temperature and pressure conditionses, in oscillating reactions device, plant base charcoal is soaked 6 hours in alkaline solution in advance, after washing to neutrality, into first paragraph HCl treatment, enter second segment phosphoric acid after filtering to handle, the 3rd section of hydrofluoric acid treatment is entered after filtering, filtration washing is packed after drying.Plant base charcoal most preferable concentrations are 10% in multistage acid cleaning process（w/v）, it is most preferably 3 hours per staging time, is repeated 3 times.Oscillating reactions device frequency of oscillation is most preferably 200 rpm.Hydrochloric acid concentration is most preferably 1 mol.L in technique‑1.Phosphoric acid concentration is most preferably 10%, and the concentration of hydrofluoric acid is most preferably 20%.The charcoal adsorption capacity that the technique results in after ultralow ash content plant base charcoal of the content of ashes below 0.1%, deliming is significantly improved.
Description
Technical field
The invention belongs to New Types of Environmental Materials and its applied technical field, the pure of plant base biological carbon materials is related generally to
Change, the method for reducing plant base charcoal content of ashes improves the adsorption capacity of plant base biological carbon materials.
Background technology
Charcoal be organic matter under anoxic or limited oxygen condition, high temperature pyrolysis formation stable aroma substance.It is biological
Charcoal, as a kind of novel carbon material, is global focus in terms of climate change, water body purification, heavy metal adsorption and soil improvement
Problem provides solution.The physical absorption that huge specific surface area is produced, charcoal are relied primarily on different from absorbent charcoal material
The widely distributed oxygen-containing functional group in surface, can produce new chemical bond with pollutant, so as to produce more stable chemistry suction
Attached effect.Therefore, as a kind of new and effective adsorbent, biological carbon materials are sent out in terms of the removal of heavy metal and organic pollution
Wave important function.In general, the preparing raw material source of charcoal is broadly divided into plant base and the major class of solid waste base 2, i.e.,
Using the Organic residues of plant as the referred to as plant base charcoal for preparing source, using organic solid waste being referred to as preparation source
For solid waste base charcoal.However, whether plant base charcoal or solid waste base charcoal, in preparation process,
In addition to charcoal product, inorganic salts, tar and other gaseous products can also be produced, these accessory substances are former together with preparing
Expect the mineralogical composition carried, be deposited in as ash content in biological carbon surface and gap structure, on the one hand ash content can shelter biology
The effect of carbon surface function functional group, on the other hand because these chemistries are more active, can influence charcoal
Adsorption efficiency.Therefore, deliming is treated as improving the key of biological carbon materials absorption property.
At present, deliming processing mainly has early stage deliming, 3 kinds of techniques of mid-term deliming and later stage deliming.Comparatively speaking, the later stage
Deliming cost is minimum, pollution is minimum, as commonly used de-ash process.Chinese Patent Application No. 200810049457.6 is used
Rinsing process, adds polyacrylamide or polyaluminium chloride flocculant in rinsing liquid, by content of ashes control below 1.5%.Specially
Sharp China's application number 201210455610.1 uses concentrated sulfuric acid acid cleaning process, and product ash content is less than 0.5%.Above-mentioned 2 patent technique
Although can preferable deliming, product ash content is still higher.Chinese Patent Application No. 201110386303.8 is located using after hydro-thermal
Science and engineering skill, after hydro-thermal alkali cleaning, hydro-thermal pickling, hot water wash, although ash content can be controlled below 0.1%, technique needs to add
Temperature pressurization, process equipment is expensive, and cost of investment is big.
In order to improve the absorption property of plant base biological carbon materials, content of ashes is at utmost reduced, the present invention is in normal temperature
Under condition of normal pressure, deliming processing, the reduction of product content of ashes are carried out to plant base charcoal using multistage pickling aftertreatment technology
To less than 0.1%.The de-ash process is simple to operate, with low cost, and deliming effect is good.
The content of the invention
The present invention improves the absorption property of charcoal, has invented a kind of many to reduce plant base charcoal content of ashes
Section pickling aftertreatment technology, thorough deliming is carried out to plant base charcoal.
The present invention is achieved by the following technical solutions, comprises the following steps：
Under normal temperature and pressure conditionses, in oscillating reactions device, plant base charcoal is soaked 6 hours in alkaline solution in advance, washed
Wash to neutrality, into first stage HCl treatment, be repeated 3 times, the processing of second stage phosphoric acid is added after, is repeated 3 times, mistake
Enter phase III hydrofluoric acid treatment after filter, be repeated 3 times, filtration washing is stored after drying.Plant base in multistage acid cleaning process
Charcoal concentration is 1-25%（w/v）, preferably 5-20%（w/v）, more preferably 10%（w/v）, it is 0.5- per staging time
5 hours, more preferably preferably 1-4 hours, 3 hours.Oscillating reactions device frequency of oscillation is 100-300 rpm, preferably 150-
250 rpm, more preferably 200 rpm.
Above-mentioned technique neutral and alkali solution is in sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium acid carbonate, ammoniacal liquor
One kind or these materials mixture, the concentration of alkali lye is 0.01-2 mol.L-1Between, preferably 0.5-1.5
mol.L-1Between, more preferably 1 mol.L-1.In technique in first paragraph pickling the concentration of hydrochloric acid in 0.1-5 mol.L-1It
Between, preferably 0.5-2 mol.L-1Between, more preferably 1 mol.L-1.In technique in second segment pickling phosphoric acid concentration
Between 1-20%, between preferably 5-15%, more preferably 10%.The concentration of hydrofluoric acid exists in the 3rd section of pickling in technique
Between 0.1-40%, between preferably 1-20%, more preferably 20%.
The plant base charcoal of above-mentioned pickling post processing is included with agricultural crop straw, fruit, branches and leaves, trees or other plant
Class organic moiety, the product after thermal cracking under limit oxygen or oxygen free condition.The plant base charcoal of preparation crosses 50 mesh sieves, and ash content contains
Measure as between 15%-35%.
The oscillating reactions device inner lining material used in above-mentioned technique is the polytetrafluoroethylmaterial material of acid-alkali-corrosive-resisting.
A kind of concrete scheme in above-mentioned technique is as follows：
Plant base charcoal alkali lye was in immersion 6 hours, after filtration washing, under normal temperature and pressure, in oscillating reactions device, vibration frequency
Under the conditions of the rpm of rate 200, the biological carbon materials after washing are inserted in oscillating reactions device, 1 mol.L is added-1Hydrochloric acid, it is biological
The concentration of charcoal is 10%（w/v）, vibrate 3 hours, be repeated 3 times, separation of solid and liquid.Then in oscillating reactions device addition 10% phosphorus
Acid, the concentration of charcoal is 10%（w/v）, vibrate 3 hours, be repeated 3 times, separation of solid and liquid.The addition 20% in oscillating reactions device
Hydrofluoric acid, the concentration of charcoal is 10%（w/v）, vibrate 3 hours, be repeated 3 times, be washed with deionized after filtering to neutrality.
After being dried to constant weight in 120 DEG C of baking ovens, it is placed in after packaging standby in drier.Soda acid liquid used can be repeated in PROCESS FOR TREATMENT
Use.
The principle of the present invention is that alkali lye reacts with the silicate and aluminosilicate inorganic salinity in biological carbon materials, and generation can
The sodium metasilicate of dissolubility or acid soluble sodium silicoaluminate.Carbonate, metal oxide and slightly solubility in biological carbon materials
Silicates material through persalt, phosphoric acid and hydrofluoric acid in the case where acting on, and gradually thoroughly dissolving enters liquid phase, then passes through filtration washing
Afterwards, separated with the armaticity solid matter in charcoal, so as to obtain the plant base biological carbon materials of ultralow content of ashes.
By the plant base charcoal of this technology PROCESS FOR TREATMENT, after first paragraph HCl treatment, content of ashes can drop
As little as 10% or so, handled by second segment phosphoric acid, ash content can be down to 1% or so, therein after the 3rd section of hydrofluoric acid treatment
Content of ashes can be reduced to less than 0.1%.With low cost, easy to operate, low for equipment requirements, the charcoal of preparation of the invention
Material ash content is ultralow, can be used for preparing ultralow ash content plant base charcoal, improves the absorption property of plant base charcoal.
Brief description of the drawings
Fig. 1 is that multistage pickling aftertreatment technology prepares ultralow ash content plant base charcoal schematic flow sheet.
Fig. 2 is that embodiment is compared figure with the maximum iodine sorption value of the charcoal for not carrying out deliming processing.
Embodiment
With reference to embodiment, the invention will be further described.
Typical process is as follows in present invention process：
Plant base charcoal → dipping by lye → chlorohydric acid pickling → phosphoric acid pickling → hydrofluoric acid pickling → separation of solid and liquid → drying →
Storage
Embodiment 1
Plant base charcoal alkali lye was in immersion 6 hours, after filtration washing, under normal temperature and pressure, in oscillating reactions device, vibration frequency
Under the conditions of the rpm of rate 200, the biological carbon materials after washing are inserted in oscillating reactions device, 1 mol.L is added-1Hydrochloric acid, it is biological
The concentration of charcoal is 10%（w/v）, vibrate 3 hours, be repeated 3 times, separation of solid and liquid.Then in oscillating reactions device addition 10% phosphorus
Acid, the concentration of charcoal is 10%（w/v）, vibrate 3 hours, be repeated 3 times, separation of solid and liquid.The addition 20% in oscillating reactions device
Hydrofluoric acid, the concentration of charcoal is 10%（w/v）, vibrate 3 hours, be repeated 3 times, be washed with deionized after filtering to neutrality.
After being dried to constant weight in 120 DEG C of baking ovens, it is placed in after packaging standby in drier.
Embodiment 2
Plant base charcoal alkali lye was in immersion 6 hours, after filtration washing, under normal temperature and pressure, in oscillating reactions device, vibration frequency
Under the conditions of the rpm of rate 100, the biological carbon materials after washing are inserted in oscillating reactions device, 0.5 mol.L is added-1Hydrochloric acid, it is raw
The concentration of thing charcoal is 20%（w/v）, vibrate 3 hours, be repeated 3 times, separation of solid and liquid.Then in oscillating reactions device addition 1% phosphorus
Acid, the concentration of charcoal is 20%（w/v）, vibrate 3 hours, be repeated 3 times, separation of solid and liquid.The hydrogen of addition 5% in oscillating reactions device
Fluoric acid, the concentration of charcoal is 20%（w/v）, vibrate 3 hours, be repeated 3 times, be washed with deionized after filtering to neutrality.
After being dried to constant weight in 120 DEG C of baking ovens, it is placed in after packaging standby in drier.
Embodiment 3
Plant base charcoal alkali lye was in immersion 6 hours, after filtration washing, under normal temperature and pressure, in oscillating reactions device, vibration frequency
Under the conditions of the rpm of rate 300, the biological carbon materials after washing are inserted in oscillating reactions device, 1mol.L is added-1Hydrochloric acid, charcoal
Concentration be 5%（w/v）, vibrate 2 hours, be repeated 3 times, separation of solid and liquid.Then in oscillating reactions device addition 10% phosphoric acid, it is raw
The concentration of thing charcoal is 5%（w/v）, vibrate 2 hours, be repeated 3 times, separation of solid and liquid.The hydrofluoric acid of addition 20% in oscillating reactions device,
The concentration of charcoal is 5%（w/v）, vibrate 2 hours, be repeated 3 times, be washed with deionized after filtering to neutrality.In 120 DEG C of bakings
It is placed in after being dried to constant weight in case, after packaging standby in drier.
Embodiment 4
Plant base charcoal alkali lye was in immersion 6 hours, after filtration washing, under normal temperature and pressure, in oscillating reactions device, vibration frequency
Under the conditions of the rpm of rate 300, the biological carbon materials after washing are inserted in oscillating reactions device, 2mol.L is added-1Hydrochloric acid, charcoal
Concentration be 5%（w/v）, vibrate 4 hours, be repeated 3 times, separation of solid and liquid.Then in oscillating reactions device addition 15% phosphoric acid, it is raw
The concentration of thing charcoal is 5%（w/v）, vibrate 4 hours, be repeated 3 times, separation of solid and liquid.The hydrofluoric acid of addition 30% in oscillating reactions device,
The concentration of charcoal is 5%（w/v）, vibrate 4 hours, be repeated 3 times, be washed with deionized after filtering to neutrality.In 120 DEG C of bakings
It is placed in after being dried to constant weight in case, after packaging standby in drier.
Embodiment 5
Plant base charcoal alkali lye was in immersion 6 hours, after filtration washing, under normal temperature and pressure, in oscillating reactions device, vibration frequency
Under the conditions of the rpm of rate 300, the biological carbon materials after washing are inserted in oscillating reactions device, 2mol.L is added-1Hydrochloric acid, charcoal
Concentration be 10%（w/v）, vibrate 1 hour, be repeated 3 times, separation of solid and liquid.Then in oscillating reactions device addition 20% phosphoric acid,
The concentration of charcoal is 10%（w/v）, vibrate 1 hour, be repeated 3 times, separation of solid and liquid.The hydrogen fluorine of addition 40% in oscillating reactions device
Acid, the concentration of charcoal is 10%（w/v）, vibrate 1 hour, be repeated 3 times, be washed with deionized after filtering to neutrality.120
After being dried to constant weight in DEG C baking oven, it is placed in after packaging standby in drier.
The testing result of ash content in the embodiment of table 1 and the charcoal for not carrying out deliming processing
| Processing | Embodiment 1 | Embodiment 2 | Embodiment 3 | Embodiment 4 | Embodiment 5 | It is untreated |
| Ash content（%） | 0.08±0.001 | 0.23±0.002 | 0.09±0.003 | 0.07±0.002 | 0.06±0.002 | 24.15±0.03 |
From the result of table 1 it is observed that make it that the content of ashes of plant base charcoal is notable using multistage pickling aftertreatment technology
Reduction, content of ashes is not more or less the same between be the same as Example, by improving oscillator vibration frequency and improving three kinds of sour uses
The charcoal content of ashes that concentration processing is obtained is minimum, and deliming effect is best.Under the premise of production cost is considered, embodiment 1
Production technology is most preferably.Fig. 2 compares to use embodiment 1-5 and not carrying out the maximum iodine sorption value of charcoal of deliming processing
Figure, it can be seen that using after de-ash process of the present invention, the absorption property of plant base charcoal can be effectively improved.
Claims (4)
1. multistage pickling aftertreatment technology prepares ultralow ash content plant base charcoal, it is characterised in that following processing step：
Under normal temperature and pressure conditionses, in oscillating reactions device, plant base charcoal is soaked 6 hours in alkaline solution in advance, washed
Wash to neutrality, entering second segment phosphoric acid into first paragraph HCl treatment, after filtering is handled, and the 3rd section of hydrofluoric acid is entered after filtering
Processing, filtration washing is packed after drying, and per 3 hours pickling processes time in stage, is repeated 3 times.
2. according to claim 1, alkaline solution be sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, sodium acid carbonate,
The mixture of one kind or these materials in ammoniacal liquor, the concentration of alkali lye is 0.01-2 mol.L-1Between, preferably 0.5-
1.5 mol.L-1Between, more preferably 1 mol.L-1。
3. according to claim 1, plant base charcoal concentration is 1-25% in technique（w/v）, preferably 5-20%（w/v）,
More preferably 10%（w/v）, it is 0.5-5 hours per staging time, preferably 1-4 hours, more preferably 3 hours, vibration was anti-
It is 100-300 rpm, more preferably preferably 150-250 rpm, 200 rpm to answer device frequency of oscillation.
4. according to claim 1, in technique in first paragraph pickling the concentration of hydrochloric acid in 0.1-5 mol.L-1Between, it is excellent
Elect 0.5-2 mol.L as-1Between, more preferably 1 mol.L-1, in technique in second segment pickling the concentration of phosphoric acid in 1-
Between 20%, between preferably 5-15%, more preferably 10%, in technique in the 3rd section of pickling the concentration of hydrofluoric acid in 0.1-
Between 40%, between preferably 1-20%, more preferably 20%.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109967034A (en) * | 2019-04-09 | 2019-07-05 | 安徽科技学院 | Final treatment techniques prepare ultralow ash content solid waste base charcoal |
| CN110589825A (en) * | 2019-10-11 | 2019-12-20 | 河南科技学院 | Preparation method of glossy privet fruit bioactive carbon |
| CN111003711A (en) * | 2019-12-04 | 2020-04-14 | 武汉热解无限能源科技有限公司 | Green preparation method of high-carbon-content porous biochar material |
| CN115555006A (en) * | 2022-11-08 | 2023-01-03 | 广东省科学院生态环境与土壤研究所 | Preparation method and application of enteromorpha biological carbon catalyst |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103979520A (en) * | 2014-04-16 | 2014-08-13 | 乌鲁木齐天合炭源化工有限公司 | Charcoal material purification method |
-
2017
- 2017-04-28 CN CN201710290487.5A patent/CN107115841A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103979520A (en) * | 2014-04-16 | 2014-08-13 | 乌鲁木齐天合炭源化工有限公司 | Charcoal material purification method |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109967034A (en) * | 2019-04-09 | 2019-07-05 | 安徽科技学院 | Final treatment techniques prepare ultralow ash content solid waste base charcoal |
| CN110589825A (en) * | 2019-10-11 | 2019-12-20 | 河南科技学院 | Preparation method of glossy privet fruit bioactive carbon |
| CN110589825B (en) * | 2019-10-11 | 2021-05-25 | 河南科技学院 | Preparation method of glossy privet fruit bioactive carbon |
| CN111003711A (en) * | 2019-12-04 | 2020-04-14 | 武汉热解无限能源科技有限公司 | Green preparation method of high-carbon-content porous biochar material |
| CN115555006A (en) * | 2022-11-08 | 2023-01-03 | 广东省科学院生态环境与土壤研究所 | Preparation method and application of enteromorpha biological carbon catalyst |
| CN115555006B (en) * | 2022-11-08 | 2023-08-15 | 广东省科学院生态环境与土壤研究所 | Preparation method and application of enteromorpha biological carbon catalyst |
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Application publication date: 20170901 |