CN109173992A - The modification peach shell method for preparation of active carbon of dibenzothiophenes in a kind of removing diesel oil - Google Patents
The modification peach shell method for preparation of active carbon of dibenzothiophenes in a kind of removing diesel oil Download PDFInfo
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- CN109173992A CN109173992A CN201811083712.9A CN201811083712A CN109173992A CN 109173992 A CN109173992 A CN 109173992A CN 201811083712 A CN201811083712 A CN 201811083712A CN 109173992 A CN109173992 A CN 109173992A
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- active carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0225—Compounds of Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt
- B01J20/0229—Compounds of Fe
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0274—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04 characterised by the type of anion
- B01J20/0296—Nitrates of compounds other than those provided for in B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3234—Inorganic material layers
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention discloses a kind of modification peach shell method for preparation of active carbon of dibenzothiophenes in removing diesel oil, this method is based on peach shell active carbon, after peach shell Activated Carbon Pretreatment, passes sequentially through acid oxidase modification and nitrate is modified, finally obtain the modification peach shell active carbon that load has metal.By electron-microscope scanning figure as can be seen that the hole quantity of peach shell active carbon obviously increases after being modified；Verification the verifying results discovery, when nitrate is the mixture of chromic nitrate and ferric nitrate, the efficiency for removing dibenzothiophenes is 55.8%, and the efficiency than unmodified active carbon removing dibenzothiophenes improves 37.4%.
Description
[technical field]
The invention belongs to modified activated carbon Material Fields, and in particular to a kind of modification peach for removing dibenzothiophenes in diesel oil
Shell method for preparation of active carbon.
[background technique]
Sulfur-containing compound in diesel oil mainly include thiophene (Thiophene, T), benzothiophene (Benzothiophene,
) and its derivative, dibenzothiophenes (Dibenzothiophene, DBT) and its derivative, mercaptan (mercaptane), sulphur BT
Ether (sulfide) and disulphide (disulfide), they are present in diesel oil in the form of respective.With diesel oil dosage
Constantly increase, the pollution of sulfide is also obvious.Peach shell active carbon phosphorus content is high, is a kind of excellent active carbon；Cause
How this, prepare satisfactory peach shell active carbon, to utilize the dibenzo thiophene in peach shell activated carbon adsorption removing diesel oil
Pheno is vital.
[summary of the invention]
It is an object of the invention to overcoming the above-mentioned prior art, dibenzothiophenes in a kind of removing diesel oil is provided
Modified peach shell method for preparation of active carbon, this method change the activated carbon modified modification peach shell active carbon as carried metal of peach shell
Property after peach shell active carbon removing dibenzothiophenes efficiency improve.
In order to achieve the above objectives, the present invention is achieved by the following scheme:
The modification peach shell method for preparation of active carbon of dibenzothiophenes in a kind of removing diesel oil, comprising the following steps:
Step 1, pretreatment peach shell active carbon, grind and screen peach shell active carbon, the peach shell active carbon after screening is cleaned
After dry, pretreated peach shell active carbon is made；
The modified peach shell activated carbon of step 2, acid oxidase, mixes pretreated peach shell active carbon and 10% nitric acid solution, water
It is cooling after bath reflux, it takes out process product A and cleans, obtain process product B after the process product A after cleaning is filtered under diminished pressure,
10% nitric acid peach shell active carbon will be made after process product B drying；
The modified peach shell activated carbon of step 3, carried metal, 10% nitric acid peach shell active carbon is put into load liquid, liquid is loaded
For chromium nitrate solution or the mixed solution of chromic nitrate and ferric nitrate；Load liquid water-bath comprising 10% nitric acid peach shell active carbon is put
It sets and is stirred on magnetic stirring apparatus, obtain suspension, process product C is obtained after suspension is filtered；Process product C is roasted,
It is filtered after cleaning, obtains process product D；Load will be obtained after process product D drying chromium or chromium-iron modification peach shell activity
Charcoal.
A further improvement of the present invention is that:
Preferably, in step 1, the standard of screening peach shell active carbon is granularity >=60 mesh.
Preferably, in step 1, by deionized water cleaning screening after peach shell active carbon, cleaning to peach shell active carbon with
Water body is layered；Drying temperature after cleaning is 120 DEG C, drying time 10h.
Preferably, in step 2, solid-liquid ratio when peach shell active carbon and 10% nitric acid solution mix is 1g:10mL.
Preferably, in step 2, water bath reflux temperature is 75 DEG C, and water-bath return time is 2h.
Preferably, in step 2, water-bath flows back process product A after cooling by deionized water cleaning, when cleaning process produces
Stop cleaning when the pH value of deionized water is neutral after object A；The drying time of process product B is 3h, and drying temperature is 25 DEG C.
Preferably, in step 3,10% nitric acid peach shell active carbon of mixing and the solid-liquid ratio for loading liquid are 1g:20mL.
Preferably, in step 3, when loading liquid is chromium nitrate solution, the concentration of chromium nitrate solution is 0.2-0.5mol/L；
When loading the mixed solution that liquid is chromic nitrate and ferric nitrate, chromium nitrate solution and iron nitrate solution mix in equal volume, and mix
The concentration of solution is 0.3mol/L.
Preferably, in step 3, magnetic agitation temperature is 25 DEG C, mixing time 12h；It is N that process product C, which roasts atmosphere,2
Atmosphere, maturing temperature are 300 DEG C, calcining time 2h；It is cleaned after roasting by deionized water, is gone after cleaning process product C
Stop cleaning when the pH value of ionized water is neutral.
Preferably, in step 3, the drying time of process product D is 3h, and drying temperature is 25 DEG C.
Compared with prior art, the invention has the following advantages:
The invention discloses a kind of modification peach shell method for preparation of active carbon of dibenzothiophenes in removing diesel oil, this method bases
In peach shell active carbon, after peach shell Activated Carbon Pretreatment, passes sequentially through acid oxidase modification and nitrate is modified, finally obtain load
There is the modification peach shell active carbon of metal.By electron-microscope scanning figure as can be seen that the hole quantity of peach shell active carbon is bright after being modified
It is aobvious to increase；Verification the verifying results discovery, when nitrate is the mixture of chromic nitrate and ferric nitrate, because containing in chromic nitrate and ferric nitrate
Trivalent chromic ion and iron ion can be attached on peach shell active carbon, a side by trivalent chromic ion and iron ion by this method
Face chromium ion and iron ion itself can adsorb dibenzothiophenes, and the on the other hand common preparation of the two has on peach shell active carbon
Synergistic effect, the two adsorb dibenzothiophenes by chemical action well；Entire preparation method is simple, it is easy to accomplish and it is former
Material is easy to get；By this method prepare be modified after peach shell active carbon, remove dibenzothiophenes efficiency be 55.8%, than
Unmodified peach shell active carbon removes the efficiency of dibenzothiophenes and improves 37.4%, and the efficiency for removing dibenzothiophenes significantly mentions
It is high.
[Detailed description of the invention]
Fig. 1 is the EDS map of Cr-Fe/ peach shell active carbon (HAC)；
Fig. 2 is unmodified peach shell active carbon electron-microscope scanning figure；
Fig. 3 is by chromic nitrate and the modified peach shell active carbon electron-microscope scanning figure of nitric acid iron mixed solution (60 μm)；
Fig. 4 is by chromic nitrate and the modified peach shell active carbon electron-microscope scanning figure of nitric acid iron mixed solution (2 μm)；
Fig. 5 is the chromatogram that GC (GC-MS gas-mass spectrometer) detects 1000ppm sample.
[specific embodiment]
Below with reference to embodiment, the invention will be described in further detail, and the invention discloses hexichol in a kind of removing diesel oil
The modification peach shell method for preparation of active carbon of bithiophene, this method specifically includes the following steps:
Step 1, pretreatment peach shell active carbon
Commercially available peach shell active carbon is ground, the peach shell active carbon greater than 60 mesh is filtered out by molecular sieve, it is anti-with deionized water
It is multiple to clean for several times, until peach shell active carbon and water body have lamination stopping cleaning being put into peach shell active carbon after removing water body
Electric heating constant-temperature blowing drying box of the temperature control at 120 DEG C, which is dried 10 hours, to be taken out for use, and it is living that pretreated peach shell is made
Property charcoal.
The modified peach shell activated carbon of step 2, acid oxidase
The nitric acid solution of the peach shell active carbon and 10% that have pre-processed, solid-liquid ratio 1g:10mL are mixed in three-necked flask；
After shaking up by flask be put into 75 DEG C of thermostatic control oscillator vibrations it is static after the 2h that flows back allow to cool to room temperature, process is produced after cooling
Object A takes out, and the process product A of taking-up is cleaned repeatedly with deionized water, and the pH value of the deionized water after cleaning is neutrality
When stop cleaning, obtain process product B after process product A after cleaning is filtered under diminished pressure, process product B be put into baking oven 25
It is taken out after dry 3h at DEG C, acquired active carbon is the modified 10% nitric acid peach shell active carbon of acid oxidase.
Step 3, carried metal are modified
10% nitric acid peach shell activated carbon is put into load liquid, load liquid is chromium nitrate solution or chromic nitrate and ferric nitrate
Mixed solution, solid-liquid ratio 1g:20mL, when loading liquid is chromium nitrate solution, the concentration of chromium nitrate solution is 0.2-0.5mol/
L；When loading the mixed solution that liquid is chromic nitrate and ferric nitrate, chromium nitrate solution and iron nitrate solution mix in equal volume, and mixed
The concentration for closing solution is 0.3mol/L；Water-bath is placed on magnetic stirring apparatus after mixing, and whipping temp is 25 DEG C, and mixing time is
12h obtains suspension after stirring；Suspension is filtered, the process product C being obtained by filtration is led into N in tube furnace2300 in atmosphere
DEG C roasting 2h, is washed with deionized, the deionized water pH value to after cleaning is neutral after taking-up；Its filter is extracted with vacuum pump
Liquid obtains process product D, and process product D is placed in drying box, obtains being loaded with corresponding gold in nitrate in 25 DEG C of dry 3h
The modification peach shell active carbon of the carried metal of category, i.e. load have chromium or chromium-iron modification peach shell active carbon.
Embodiment 1
Step 1, pretreatment peach shell active carbon
Commercially available peach shell active carbon is ground, the peach shell active carbon greater than 60 mesh is filtered out by molecular sieve, it is anti-with deionized water
It is multiple to clean for several times, until peach shell active carbon and water body have lamination stopping cleaning being put into peach shell active carbon after removing water body
Electric heating constant-temperature blowing drying box of the temperature control at 120 DEG C, which is dried 10 hours, to be taken out for use.
The modified peach shell activated carbon of step 2, acid oxidase
The nitric acid solution of the peach shell active carbon and 10% that have pre-processed, solid-liquid ratio 1g:10mL are mixed in three-necked flask；
After shaking up by flask be put into 75 DEG C of thermostatic control oscillator vibrations it is static after the 2h that flows back allow to cool to room temperature, process is produced after cooling
Object A takes out, and the process product A of taking-up is cleaned repeatedly with deionized water, goes until with pH tester test cleaning process product A
Stop cleaning when the pH value of ionized water is neutral, process product B is obtained after process product A after cleaning is filtered under diminished pressure, by process
Product B takes out after being put into baking oven at 25 DEG C dry 3h, and acquired active carbon is that the modified 10% nitric acid peach shell of acid oxidase is living
Property charcoal.
Step 3, the chromium nitrate solution that concentration is 0.2mol/L are modified
10% nitric acid peach shell activated carbon is put into the chromium nitrate solution that concentration is 0.2mol/L, solid-liquid ratio 1g:20mL；
Water-bath is placed on magnetic stirring apparatus after mixing, and whipping temp is 25 DEG C, and mixing time 12h obtains suspension after stirring；It will
Suspension filtering, leads to N in tube furnace for the process product C being obtained by filtration2300 DEG C of roasting 2h, use deionization after taking-up in atmosphere
Water washing, until the deionized water pH value after cleaning is neutrality；Its filtrate is extracted with vacuum pump, process product D is obtained, process is produced
Object D is placed in drying box, obtains the modification peach shell active carbon that load has chromium in 25 DEG C of dry 3h.
Embodiment 2
Step 1, pretreatment peach shell active carbon
Commercially available peach shell active carbon is ground, the peach shell active carbon greater than 60 mesh is filtered out by molecular sieve, it is anti-with deionized water
It is multiple to clean for several times, until peach shell active carbon and water body have lamination stopping cleaning being put into peach shell active carbon after removing water body
Electric heating constant-temperature blowing drying box of the temperature control at 120 DEG C, which is dried 10 hours, to be taken out for use.
The modified peach shell activated carbon of step 2, acid oxidase
The nitric acid solution of the peach shell active carbon and 10% that have pre-processed, solid-liquid ratio 1g:10mL are mixed in three-necked flask；
After shaking up by flask be put into 75 DEG C of thermostatic control oscillator vibrations it is static after the 2h that flows back allow to cool to room temperature, process is produced after cooling
Object A takes out, and the process product A of taking-up is cleaned repeatedly with deionized water, goes until with pH tester test cleaning process product A
Stop cleaning when the pH value of ionized water is neutral, process product B is obtained after process product A after cleaning is filtered under diminished pressure, by process
Product B takes out after being put into baking oven at 25 DEG C dry 3h, and acquired active carbon is that the modified 10% nitric acid peach shell of acid oxidase is living
Property charcoal.
Step 3, the chromium nitrate solution that concentration is 0.5mol/L are modified
10% nitric acid peach shell activated carbon is put into the chromium nitrate solution that concentration is 0.5mol/L, solid-liquid ratio 1g:20mL；
Water-bath is placed on magnetic stirring apparatus after mixing, and whipping temp is 25 DEG C, mixing time 12h；Suspension is obtained after stirring；It will
Suspension filtering, leads to N in tube furnace for the process product C being obtained by filtration2300 DEG C of roasting 2h, use deionization after taking-up in atmosphere
Water washing, until the deionized water pH value after cleaning is neutrality；Its filtrate is extracted with vacuum pump, process product D is obtained, process is produced
Object D is placed in drying box, obtains the modification peach shell active carbon that load has chromium in 25 DEG C of dry 3h.
Embodiment 3
Step 1, pretreatment peach shell active carbon
Commercially available peach shell active carbon is ground, the peach shell active carbon greater than 60 mesh is filtered out by molecular sieve, it is anti-with deionized water
It is multiple to clean for several times, until peach shell active carbon and water body have lamination stopping cleaning being put into peach shell active carbon after removing water body
Electric heating constant-temperature blowing drying box of the temperature control at 120 DEG C, which is dried 10 hours, to be taken out for use.
The modified peach shell activated carbon of step 2, acid oxidase
The nitric acid solution of the peach shell active carbon and 10% that have pre-processed, solid-liquid ratio 1g:10mL are mixed in three-necked flask；
After shaking up by flask be put into 75 DEG C of thermostatic control oscillator vibrations it is static after the 2h that flows back allow to cool to room temperature, process is produced after cooling
Object A takes out, and the process product A of taking-up is cleaned repeatedly with deionized water, goes until with pH tester test cleaning process product A
Stop cleaning when the pH value of ionized water is neutral, process product B is obtained after process product A after cleaning is filtered under diminished pressure, by process
Product B takes out after being put into baking oven at 25 DEG C dry 3h, and acquired active carbon is that the modified 10% nitric acid peach shell of acid oxidase is living
Property charcoal.
Step 3, the chromium nitrate solution that concentration is 0.2mol/L are modified
10% nitric acid peach shell activated carbon is put into the chromium nitrate solution that concentration is 0.4mol/L, solid-liquid ratio 1g:20mL；
Water-bath is placed on magnetic stirring apparatus after mixing, and whipping temp is 25 DEG C, and mixing time 12h obtains suspension after stirring；It will
Suspension filtering, leads to N in tube furnace for the process product C being obtained by filtration2300 DEG C of roasting 2h, use deionization after taking-up in atmosphere
Water washing, until the deionized water pH value after cleaning is neutrality；Its filtrate is extracted with vacuum pump, process product D is obtained, process is produced
Object D is placed in drying box, obtains the modification peach shell active carbon that load has chromium in 25 DEG C of dry 3h.
Embodiment 4
Step 1, pretreatment peach shell active carbon
Commercially available peach shell active carbon is ground, the peach shell active carbon greater than 60 mesh is filtered out by molecular sieve, it is anti-with deionized water
It is multiple to clean for several times, until peach shell active carbon and water body have lamination stopping cleaning being put into peach shell active carbon after removing water body
Electric heating constant-temperature blowing drying box of the temperature control at 120 DEG C, which is dried 10 hours, to be taken out for use.
The modified peach shell activated carbon of step 2, acid oxidase
The nitric acid solution of the peach shell active carbon and 10% that have pre-processed, solid-liquid ratio 1g:10mL are mixed in three-necked flask；
After shaking up by flask be put into 75 DEG C of thermostatic control oscillator vibrations it is static after the 2h that flows back allow to cool to room temperature, process is produced after cooling
Object A takes out, and the process product A of taking-up is cleaned repeatedly with deionized water, goes until with pH tester test cleaning process product A
Stop cleaning when the pH value of ionized water is neutral, process product B is obtained after process product A after cleaning is filtered under diminished pressure, by process
Product B takes out after being put into baking oven at 25 DEG C dry 3h, and acquired active carbon is that the modified 10% nitric acid peach shell of acid oxidase is living
Property charcoal.
Step 3, the chromic nitrate that concentration is 0.3mol/L and nitric acid iron mixed solution are modified
10% nitric acid peach shell activated carbon is put into the mixed liquor that chromic nitrate and ferric nitrate mix in equal volume, mixed solution
Concentration is 0.3mol/L, solid-liquid ratio 1g:20mL；Water-bath is placed on magnetic stirring apparatus after mixing evenly, whipping temp 25
DEG C, mixing time is to obtain suspension after 12h is stirred；Suspension is filtered, the process product C being obtained by filtration is led in tube furnace
N2300 DEG C of roasting 2h, are washed with deionized after taking-up in atmosphere, until the deionized water pH value after cleaning is neutrality；Use vacuum
Pumping takes its filtrate, obtains process product D, and process product D is placed in drying box, and obtaining load in 25 DEG C of dry 3h has
Chromium-iron modification peach shell active carbon.
As shown in Figure 1, the load that embodiment 4 is prepared has the modification peach shell active carbon of chromium ion and iron ion to pass through
Its constituent content of EDS atlas analysis, shown in result table 1, it can be seen that Cr content is 7.17%, Fe content from Fig. 1 and table 1
It is 1.80%, illustrates that there are Cr and Fe elements in modified activated carbon.
The EDS atlas analysis and its constituent content of 1 Cr-Fe/HAC of table
| Element | C | O | Cr | Fe |
| Linear system type | K linear system | K linear system | L linear system | L linear system |
| Mass percentage, % | 78.13 | 12.90 | 7.17 | 1.80 |
| Atomic percent | 86.30 | 10.68 | 1.83 | 1.19 |
Fig. 3 and Fig. 4 is to be carried out the chromic nitrate of 0.3mol/L and the modified peach shell of nitric acid iron mixed solution in example 4 to live
Property charcoal electron-microscope scanning figure (amplification factor different), comparison diagram 2 is it can be found that the hole of the peach shell active carbon after being modified is obvious
Increase, hole quantity increases, and hole depth is deeper.
Compliance test result
Metal peach shell active carbon modified in above-described embodiment is subjected to compliance test result by following step.
Modified carried metal peach shell active carbon is placed in the mould oil that concentration is 1000ppm, modified peach shell activity
The ratio of charcoal and mould oil is 1g:25mL, and mould oil is the solution that dibenzothiophenes (DBT) and n-hexane are prepared；After mixing often
After continuously stirring 2h under normal temperature and pressure, successively with common funnel, sand core funnel and 0.45 micrometer Millipore connect circulating vacuum pump into
Row filters, and filters out adsorbent, and it is to be measured to obtain sample.
Sample is measured to the size of peak area by gas-chromatography, sample residue sulphur is obtained according to calibration curve equation
Content, to further calculate de- dibenzothiophenes rate.Specific step is as follows:
(1) analysis condition are as follows:
The measurement of sulfur content in DBT model oil samples is carried out by Shimadzu gas chromatograph, which is equipped with hydrogen
Flame ignition, nitrogen buffer gas, injection port select split sampling mode, and split ratio is set as 50:1, meanwhile, each sample introduction
Sample volume is 0.5 μ L.
(2) testing conditions (dibenzothiophenes sulfur compound) are as follows:
Chromatographic column: selection polarity capillary column SE-54；Split sampling；Sample introduction ratio is 50:1；Injector temperature is 340 DEG C；
Column temperature is 230 DEG C；Detector temperature is 230 DEG C；Sample volume is 0.5 microlitre；Detection time is 8min；Clipping time is
3.5min.GC detects 1000ppm sample referring to Fig. 5.
(3) dibenzothiophenes rate is taken off are as follows: η=[(CBegin-CEnd)/CBegin] × 100%
Wherein: CBeginIndicate the concentration of dibenzothiophenes before adsorbing；
CEndIndicate the concentration of dibenzothiophenes after adsorbing；
η indicates de- dibenzothiophenes rate (%)
Hexichol is taken off to the absorption of DBT mould oil for unmodified peach shell active carbon, embodiment 2 and embodiment 3 as shown in table 2
Bithiophene effect.In conjunction with table 1 as can be seen that being modified the de- dibenzothiophenes of rear peach shell activated carbon adsorption therewith by surveying gas phase
Before the unmodified peach shell active carbon that measures take off the efficiency of dibenzothiophenes and compare, take off dibenzothiophenes Contrast on effect: Cr-Fe/HAC
> Cr-HAC > AC.
2 supported ionic active carbon of table and unmodified comparison
| Sample | AC | Embodiment 2, Cr-HAC | Embodiment 4, Cr-Fe/HAC |
| De- dibenzothiophenes rate | 18.4% | 44.5% | 55.8% |
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 (10)
1. the modification peach shell method for preparation of active carbon of dibenzothiophenes in a kind of removing diesel oil, which is characterized in that including following step
It is rapid:
Step 1, pretreatment peach shell active carbon, grind and screen peach shell active carbon, will dry after the peach shell active carbon cleaning after screening
It is dry, pretreated peach shell active carbon is made；
The modified peach shell activated carbon of step 2, acid oxidase, mixes pretreated peach shell active carbon and 10% nitric acid solution, and water-bath is returned
It is cooling after stream, it takes out process product A and cleans, obtain process product B after the process product A after cleaning is filtered under diminished pressure, incited somebody to action
10% nitric acid peach shell active carbon is made after journey product B is dry；
The modified peach shell activated carbon of step 3, carried metal, 10% nitric acid peach shell active carbon is put into load liquid, and load liquid is nitre
The mixed solution of sour chromium solution or chromic nitrate and ferric nitrate；Load liquid water-bath comprising 10% nitric acid peach shell active carbon is placed on
It is stirred on magnetic stirring apparatus, obtains suspension, process product C is obtained after suspension is filtered；Process product C is roasted, is cleaned
After filter, obtain process product D；There are chromium or chromium-iron modification peach shell active carbon for load is obtained after process product D drying.
2. the modification peach shell method for preparation of active carbon of dibenzothiophenes in a kind of removing diesel oil according to claim 1,
It is characterized in that, in step 1, the standard of screening peach shell active carbon is granularity >=60 mesh.
3. the modification peach shell method for preparation of active carbon of dibenzothiophenes in a kind of removing diesel oil according to claim 1,
It is characterized in that, in step 1, by the peach shell active carbon after deionized water cleaning screening, cleaning goes out to peach shell active carbon with water body
Now it is layered；Drying temperature after cleaning is 120 DEG C, drying time 10h.
4. the modification peach shell method for preparation of active carbon of dibenzothiophenes in a kind of removing diesel oil according to claim 1,
It is characterized in that, in step 2, solid-liquid ratio when peach shell active carbon and 10% nitric acid solution mix is 1g:10mL.
5. the modification peach shell method for preparation of active carbon of dibenzothiophenes in a kind of removing diesel oil according to claim 1,
It is characterized in that, in step 2, water bath reflux temperature is 75 DEG C, and water-bath return time is 2h.
6. the modification peach shell method for preparation of active carbon of dibenzothiophenes in a kind of removing diesel oil according to claim 1,
It is characterized in that, in step 2, water-bath flows back process product A after cooling through deionized water cleaning, after cleaning process product A
Stop cleaning when the pH value of deionized water is neutral；The drying time of process product B is 3h, and drying temperature is 25 DEG C.
7. the modification peach shell method for preparation of active carbon of dibenzothiophenes in a kind of removing diesel oil according to claim 1,
It is characterized in that, in step 3,10% nitric acid peach shell active carbon of mixing and the solid-liquid ratio for loading liquid are 1g:20mL.
8. the modification peach shell method for preparation of active carbon of dibenzothiophenes in a kind of removing diesel oil according to claim 1,
It is characterized in that, in step 3, when loading liquid is chromium nitrate solution, the concentration of chromium nitrate solution is 0.2-0.5mol/L；Work as load
When liquid is the mixed solution of chromic nitrate and ferric nitrate, chromium nitrate solution and iron nitrate solution mix in equal volume, and mixed solution
Concentration is 0.3mol/L.
9. the modification peach shell method for preparation of active carbon of dibenzothiophenes in a kind of removing diesel oil according to claim 1,
It is characterized in that, in step 3, magnetic agitation temperature is 25 DEG C, mixing time 12h；It is N that process product C, which roasts atmosphere,2Atmosphere,
Maturing temperature is 300 DEG C, calcining time 2h；It is cleaned after roasting by deionized water, deionized water after cleaning process product C
PH value stop cleaning when being neutral.
10. according to claim 1 described in -9 any one in a kind of removing diesel oil dibenzothiophenes modification peach shell active carbon
Preparation method, which is characterized in that in step 3, the drying time of process product D is 3h, and drying temperature is 25 DEG C.
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