CN108421530A - A kind of ultralow ash content semicoke and preparation method thereof - Google Patents
A kind of ultralow ash content semicoke and preparation method thereof Download PDFInfo
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- CN108421530A CN108421530A CN201810340622.7A CN201810340622A CN108421530A CN 108421530 A CN108421530 A CN 108421530A CN 201810340622 A CN201810340622 A CN 201810340622A CN 108421530 A CN108421530 A CN 108421530A
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- semicoke
- deliming
- ash content
- obtains
- flotation
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- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- 239000002956 ash Substances 0.000 claims abstract description 131
- 239000002245 particle Substances 0.000 claims abstract description 111
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 100
- 238000005188 flotation Methods 0.000 claims abstract description 83
- 238000000034 method Methods 0.000 claims abstract description 81
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 60
- 239000012065 filter cake Substances 0.000 claims abstract description 42
- 235000002918 Fraxinus excelsior Nutrition 0.000 claims abstract description 32
- 238000000967 suction filtration Methods 0.000 claims abstract description 30
- 239000000126 substance Substances 0.000 claims abstract description 23
- 239000002994 raw material Substances 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 8
- 239000002002 slurry Substances 0.000 claims description 70
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 69
- 239000000706 filtrate Substances 0.000 claims description 61
- 230000008569 process Effects 0.000 claims description 29
- 238000012545 processing Methods 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910000040 hydrogen fluoride Inorganic materials 0.000 claims description 17
- 239000012535 impurity Substances 0.000 claims description 16
- 239000000843 powder Substances 0.000 claims description 15
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 12
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 12
- 150000003839 salts Chemical class 0.000 claims description 11
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000004088 foaming agent Substances 0.000 claims description 10
- 239000004094 surface-active agent Substances 0.000 claims description 10
- 238000005273 aeration Methods 0.000 claims description 8
- 239000002283 diesel fuel Substances 0.000 claims description 8
- GPRLSGONYQIRFK-MNYXATJNSA-N triton Chemical compound [3H+] GPRLSGONYQIRFK-MNYXATJNSA-N 0.000 claims description 8
- SJWFXCIHNDVPSH-UHFFFAOYSA-N octan-2-ol Chemical group CCCCCCC(C)O SJWFXCIHNDVPSH-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 3
- 238000013459 approach Methods 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000010521 absorption reaction Methods 0.000 abstract description 19
- 238000005406 washing Methods 0.000 abstract description 13
- 229960002050 hydrofluoric acid Drugs 0.000 description 40
- 239000007789 gas Substances 0.000 description 20
- BFXAWOHHDUIALU-UHFFFAOYSA-M sodium;hydron;difluoride Chemical compound F.[F-].[Na+] BFXAWOHHDUIALU-UHFFFAOYSA-M 0.000 description 20
- 238000006243 chemical reaction Methods 0.000 description 14
- 229910052500 inorganic mineral Inorganic materials 0.000 description 14
- 239000010410 layer Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 10
- 229910052739 hydrogen Inorganic materials 0.000 description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- 239000002253 acid Substances 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 238000001179 sorption measurement Methods 0.000 description 9
- 235000013305 food Nutrition 0.000 description 8
- 239000011707 mineral Substances 0.000 description 8
- 239000011148 porous material Substances 0.000 description 8
- 238000010306 acid treatment Methods 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- 239000003814 drug Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000003682 fluorination reaction Methods 0.000 description 6
- 229910021532 Calcite Inorganic materials 0.000 description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 239000008280 blood Substances 0.000 description 5
- 210000004369 blood Anatomy 0.000 description 5
- 230000008859 change Effects 0.000 description 5
- 235000012239 silicon dioxide Nutrition 0.000 description 5
- 238000002336 sorption--desorption measurement Methods 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 238000001784 detoxification Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- 239000000377 silicon dioxide Substances 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- IJKVHSBPTUYDLN-UHFFFAOYSA-N dihydroxy(oxo)silane Chemical compound O[Si](O)=O IJKVHSBPTUYDLN-UHFFFAOYSA-N 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- KBPLFHHGFOOTCA-UHFFFAOYSA-N 1-Octanol Chemical group CCCCCCCCO KBPLFHHGFOOTCA-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 2
- 229910052622 kaolinite Inorganic materials 0.000 description 2
- 210000003734 kidney Anatomy 0.000 description 2
- 210000004185 liver Anatomy 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- -1 cyclic amino acid Chemical class 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- WWRCTCWJBIULBY-UHFFFAOYSA-N disodium oxygen(2-) hydrate Chemical compound O.[O-2].[Na+].[Na+] WWRCTCWJBIULBY-UHFFFAOYSA-N 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 210000003739 neck Anatomy 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 150000004053 quinones Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- ABTOQLMXBSRXSM-UHFFFAOYSA-N silicon tetrafluoride Chemical compound F[Si](F)(F)F ABTOQLMXBSRXSM-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
-
- 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
- B01J20/3071—Washing or leaching
-
- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
Abstract
The invention discloses a kind of ultralow ash content semicokes and preparation method thereof, include the chemical deliming of the crushing of raw material semicoke particle, the flotation deliming of semicoke particle, flotation deliming semicoke, comprise the concrete steps that：First raw material semicoke particle is crushed to obtain semicoke particle, deliming is carried out with flotation deliming method to semicoke particle, obtain flotation deliming semicoke, then to flotation deliming semicoke hydrofluoric acid deliming, again deliming is carried out with hydrochloric acid, suction filtration obtains filter cake, to filter cake washing, drying, you can obtain ultralow ash content semicoke.Ultralow ash content semicoke content of ashes prepared by the present invention is minimum to can reach 0.20%, compared with semicoke, the specific surface area with bigger and stronger absorption property.
Description
Technical field
The invention belongs to technical field of coal chemical industry, and in particular to a kind of ultralow ash content semicoke and preparation method thereof.
Background technology
Semicoke be coal at a lower temperature（600 DEG C~700 DEG C）The product of pyrolysis, main component are carbon, Ke Yizuo
It is used for high-quality carbon source, is mainly used for domestic fuel and power generation.However since semicoke ash content is higher, fuel or use can only be used as
It generates electricity, added value is relatively low, and purposes is limited.In recent years, many grind has been carried out to preparing active carbocoal using semicoke both at home and abroad
Study carefully.Active carbocoal is widely used, simple production process, has good economic value, is that the high value added utilization of semicoke is developed
One new direction.
However, containing higher ash content in semicoke particle, the main component of ash content is inorganic mineral, and inorganic mineral is verified
It is influenced greatly in the performance of active carbocoal, and then limits application of the active carbocoal in the stringent field of content of ashes requirement.Than
Such as, the fields such as medicine, food, it is higher for the content requirement of the ash content of active carbocoal；Because medicine, food and people it is strong
Health is closely bound up, if active carbocoal content of ashes is higher, active carbocoal absorption property is with regard to poor, the suction to contaminant particle
Attached processing is just not thorough, and causes the reduction of medicine, food hygiene；, whereas if active carbocoal content of ashes is lower, adsorptivity
Can be better, stronger to the adsorption capacity of contaminant particle, this can give the health of medicine, field of food higher
It ensures；Certainly, ash content is lower, and active carbocoal can also utilize strong adsorptivity that preservation is dried to medicine, food.It is sharp for another example
It is decolourized taste removal to sake with high ash content active carbocoal, the inorganic mineral in ash content can allow ethyl alcohol at a certain temperature
Catalysis reaction occurs, forms acetaldehyde and CO2, the quality of wine is made to reduce；In addition, if the iron being dissolved out in ash content is more than
0.025%, iron may can be reacted with the cyclic amino acid in wine generates foxy coloring matter；It does not decolourize not only but also makes
The color burn of wine.
Also in active carbocoal preparation process, semicoke particle poration process can be by the shadow of the inorganic mineral in ash content
It rings, is unfavorable for the development in hole.Wigmans T have found：The growth effect of inorganic mineral device to hole is very big, it promotes aperture to become larger,
Big hole number in increasing causes active carbocoal entirety specific surface area to become smaller, and eventually leads to active carbocoal entirety adsorption capacity drop
It is low.
In recent years, the research of Absorption Type Blood Detoxifier-Initial is just carried out extensively in the world, and is formally applied to face
Bed, the active carbocoal of high adsorption are applied well wherein；And the minimum semicoke of content of ashes will be used as and prepare high absorption
The optimum feed stock of property active carbocoal, this for future studies first aid detoxification device, absorbent-type artificial kidney, artificial liver it is main
Component etc. is very helpful.
As long as and prepare the semicoke of ultralow content of ashes, then activated, so that it may prepare the work of ultralow content of ashes
Property semicoke, therefore, the reduction of semicoke content of ashes is for preparing active carbocoal and active carbocoal in fields such as medicine, food
Extensive use is vital.
It is existing application No. is：201410421871.0 the application documents of entitled " a kind of chemical deliming method of semicoke "
In, NaOH delimings are first passed through to semicoke, then neutralized with single hydrochlorate acid, the reaction condition of NaOH requires stringent in the method, special
It is not that reaction temperature needs carry out at 300~450 DEG C；And, semicoke particle and hydrogen very more to the usage amount of sodium hydroxide
Sodium oxide molybdena in proportion 1:(1~3) is reacted, and can bring the raising of cost in this way；Meanwhile the waste liquid generated in preparation process compared with
It is more, and do not handle reasonably, the waste of resource is caused, pollution also is brought to environment.
It is entitled application No. is 201610063655.2：A kind of preparation method of ultrapure active carbocoal, this application documents
In, the semicoke content of ashes prepared is not more than 4%；It is that NaOH deliming processing is first carried out to the semicoke after activation, then again
It is handled through ash removal by HCl, the semicoke content of ashes prepared is relatively low, reaches the standard of ultrapure semicoke, can also be played to sewage disposal
Certain effect；But the semicoke application surface of this purity or relatively narrow, there is limitation, it can not be in necks such as medical treatment, food
Domain obtains larger range of application, and especially in terms of the research of Absorption Type Blood Detoxifier-Initial, limitation embodies more bright
It is aobvious；Moreover, not taking corresponding recycling measure for the intermediate product in preparation process, the wave of resource is caused
Take, is also unfavorable for environmental protection.
Invention content
In order to solve above-mentioned problems of the prior art, the present invention provides a kind of ultralow ash content semicoke and its preparations
Method, it is relatively low that there is this kind of method deliming rate height, reaction condition to require, intermediate product recycling rate height, environmental pollution
Small advantage, prepared ultralow ash content semicoke content of ashes is extremely low, and absorption property is good, and application surface is wider.
The technical problem to be solved in the present invention is achieved through the following technical solutions：
A kind of preparation method of ultralow ash content semicoke, this approach includes the following steps：
Step 1, the crushing of raw material semicoke particle：Raw material semicoke particle is crushed to the semicoke particle that diameter is not more than 0.5mm；
Step 2, the flotation deliming of semicoke particle：The semicoke particle that step 1 obtains is subjected to deliming processing with flotation deliming method,
Obtain flotation deliming semicoke；
Step 3, the chemical deliming of semicoke：The flotation deliming semicoke that step 2 obtains is subjected to deliming processing with chemical deliming method,
Obtain ultralow ash content semicoke；
The detailed process of chemical deliming method in step 3 is：
Step 1, flotation deliming semicoke flotation deliming method handled first temperature be 40 DEG C~60 DEG C, it is a concentration of
In 0.5mol/L~6mol/L hydrofluoric acid solutions, 1.5~3h is impregnated, is then filtered, washed, obtain semicoke A；
Step 2, the semicoke A that will be obtained in step 1 impregnates in a concentration of 5mol/L sodium hydroxide solutions, filters, is washed to filter
Liquid is in neutrality, and suction filtration obtains filter cake, and filter cake is dried；
Step 3, filter cake step 2 obtained is first 40 DEG C~60 DEG C, the hydrochloric acid of a concentration of 4mol/L~10mol/L in temperature
In solution, 1~4h is impregnated, is then filtered, washed, obtain semicoke B；
Step 4, the semicoke B that step 3 obtains impregnated in a concentration of 5mol/L sodium hydroxide solutions, be washed to during filtrate is in
Property, suction filtration obtains filter cake, is dried to filter cake, obtains ultralow ash content semicoke.
Preferably, the detailed process of flotation deliming method is in the step 2：
Step（1）, the semicoke particles with water that the step 1 is obtained dilutes, and obtains the first slurries；
Step（2）, surfactant is added in first slurries, obtains the second slurries；
Step（3）, collecting agent is added in second slurries, obtains third slurries；
Step（4）, foaming agent is added in the third slurries, obtain upper layer be covered with semicoke bubble and lower layer be impurity
4th slurries；
Step（5）, the bubble for being covered with semicoke and impurity of the 4th slurries are detached, the semicoke isolated is carried out again
Dehydration, drying, obtain flotation deliming semicoke.
Preferably, the surfactant is triton x-100；The collecting agent is 0#Diesel oil；The foaming agent is secondary
Octanol.
Preferably, the flotation deliming method is in flotation device rotating speed 1800r/min, aeration quantity 0.21m3Under conditions of/h into
Capable.
Preferably, the time impregnated in sodium hydroxide solution in the step 2 is 20min；
Preferably, the time impregnated in sodium hydroxide solution in the step 4 is 30min；
Preferably, it is filtered in the step 1 and NaF powder is added in obtained filtrate, then heated at a temperature of 360 DEG C, recycled
Hydrogen fluoride.
Preferably, it is filtered in the step 3 in obtained filtrate and salt is added, filtrate is distilled, recycle hydrogen chloride.
The invention also includes ultralow ash content semicoke made from any of the above-described kind of method, the ultralow ash content semicoke content of ashes
It is minimum to reach 0.20%.
Compared with prior art, beneficial effects of the present invention：
1, the present invention carries out deliming processing by choosing optimal preparation condition to semicoke, first by flotation deliming method to semicoke
Particle carries out thick deliming, the corrosivity and permeability for then utilizing hydrofluoric acid extremely strong, is difficult to thoroughly to remove to hydrochloric acid in ash content
The minerals such as kaolinite, quartz, calcite are thoroughly removed, and then recycle hydrochloric acid to generation during hydrofluoric acid deliming
Calcirm-fluoride, ferric flouride etc. are dissolved, meanwhile, the carbonate in the calcite that hydrochloric acid does not also remove hydrofluoric acid and major part
Sulfate dissolves.The semicoke content of ashes being prepared out is lower, semicoke purity higher, to further prepare active carbocoal,
And preferably application provides technical foundation to active carbocoal, is especially ground in medical treatment such as food storage, absorbent-type blood detoxifications
Application in studying carefully.
2, for the present invention during preparing ultralow ash content semicoke, hydrofluoric acid and ash removal by HCl reaction temperature are 40 DEG C~60
Between DEG C, reaction condition requires low；Again because semicoke has first got rid of a part of ash content through flotation deliming, then through hydrofluoric acid and salt
During sour deliming, the dosage of a part of acid can be saved.
3, the ultralow ash content semicoke prepared by the present invention is handled by the deep cleaning of flotation deliming and composite strong acid,
The intragranular ash content of semicoke almost can be removed thoroughly so that semicoke particle internal void increases, and specific surface area increases, aperture
Become smaller, further enhances the absorption property of semicoke particle.
4, in the filtrate that step 1 of the present invention obtains after filtering, NaF powder is added, NaF occurs with the hydrogen fluoride in filtrate
Chemisorption, specially：Then by being heated desorption reaction to filtrate occurs for NaF+HF → NaHF2, specially：
NaHF2→ NaF+HF, and then hydrogen fluoride gas and NaF are recycled, moreover, hydrogen fluoride gas and NaF can be recycled again so that
Resource can be reasonably and effectively used；Avoid the pollution of environment.
Equally, in the filtrate obtained after step 3 of the present invention suction filtration, salt is added can be by chlorine by being distilled to filtrate
Change hydrogen to be recycled, and then utilizes again.
Description of the drawings
Fig. 1 is the preparation technology flow chart of the ultralow ash content semicoke of the present invention；
Fig. 2 is present invention semicoke particle content of ashes change curve after hydrofluoric acid treatment；
Fig. 3 is present invention semicoke particle content of ashes change curve after HCl treatment；
Fig. 4 is the XRD diagram of ultralow ash content semicoke particle and semicoke particle prepared by the embodiment of the present invention 4；
Fig. 5 is ultralow ash content semicoke particle and semicoke particle N prepared by the embodiment of the present invention 42Adsorption desorption isothermal curve；
Fig. 6 is ultralow ash content semicoke particle and semicoke particle graph of pore diameter distribution prepared by the embodiment of the present invention 4；
Fig. 7 is the infrared spectrogram of ultralow ash content semicoke particle and semicoke prepared by the embodiment of the present invention 4.
Specific implementation mode
Further detailed description is done to the present invention with reference to specific embodiment, but embodiments of the present invention are not limited to
This.
Embodiment 1：
A kind of preparation method of ultralow ash content semicoke, includes the following steps：
Step 1, the crushing of raw material semicoke particle：Raw material semicoke particle is crushed to the semicoke particle that diameter is not more than 0.5mm；
Detailed process is：Using quartering division sample, first uses jaw crusher moderately broken, is then crushed with ball mill,
Finally the semicoke after crushing is sieved successively with the sieve of 0.5mm, 0.25mm, 0.125mm, 0.074mm, to that cannot penetrate
The semicoke particle of 0.5mm sieves is further crushed, until ensuring that all samples can be transferred through sieve；
Step 2, the flotation deliming of semicoke particle：The semicoke particle that step 1 obtains is subjected to deliming processing with flotation deliming method,
Obtain flotation deliming semicoke；
Two flotation deliming method of above-mentioned steps is in flotation device rotating speed 1800r/min, aeration quantity 0.21m3It is carried out under conditions of/h,
Detailed process is：
Step（1）, the semicoke particles with water that step 1 is obtained dilutes, and obtains the first slurries, the first concentration of slurry is 60g/L；
Step（2）, surfactant triton x-100 is added in the first slurries, obtains the second slurries；
Step（3）, collecting agent 0 is added in the second slurries#Diesel oil obtains third slurries；
Step（4）, in third slurries be added foaming agent sec-octyl alcohol, obtain upper layer be covered with semicoke bubble and lower layer be impurity
The 4th slurries；
Step（5）, the bubble for being covered with semicoke and impurity of the 4th slurries are detached, the semicoke isolated is taken off again
Water, drying obtain flotation deliming semicoke.
The flotation deliming semicoke that step 2 obtains is carried out deliming processing with chemical deliming method, obtains ash content and contain by step 3
Ultralow ash content semicoke of the amount less than 1%；
The detailed process of chemical deliming method in step 3 is：
Step 1, it is first 40 DEG C, a concentration of 0.5mol/L hydrogen fluorine in temperature by the flotation deliming semicoke that flotation deliming method is handled
In acid solution, 3h is impregnated, is filtered, washing obtains semicoke A；
Step 2, the semicoke A that will be obtained in step 1 impregnates 20min, filtering, water in a concentration of 5mol/L sodium hydroxide solutions
It is washed till filtrate to be in neutrality, suction filtration obtains filter cake, and filter cake is dried；
Step 3, filter cake step 2 obtained is first 40 DEG C, in the hydrochloric acid solution of a concentration of 4mol/L in temperature, impregnates 4h, take out
Filter, washing, obtains semicoke B；
Step 4, the semicoke B that step 3 obtains in a concentration of 5mol/L sodium hydroxide solutions impregnated into 30min, be washed to filtrate
It is in neutrality, suction filtration obtains filter cake, and filter cake is dried, and obtained semicoke content of ashes is 2.15%.
NaF powder is added in the filtrate obtained after the suction filtration of above-mentioned steps 1, then filtrate is heated at a temperature of 360 DEG C
Hydrogen fluoride gas in filtrate can be pyrolyzed out by 2h；The fluorination hydrogen retrieval being pyrolyzed out is got up to recycle.
Specifically reactive mode is：NaF+HF→NaHF2
NaHF2→NaF+HF
Reaction detailed process is above:NaF occurs Chemisorption with the hydrofluoric acid in filtrate first and generates NaHF2, then
Under 360 DEG C of high temperature action, NaHF2It can be pyrolyzed as NaF powder and hydrogen fluoride gas.
Salt is added in the filtrate obtained after the suction filtration of above-mentioned steps 3, then filtrate is distilled, obtains hydrogen chloride gas
Body is recycled.
Embodiment 2：
A kind of preparation method of ultralow ash content semicoke, includes the following steps：
Step 1, the crushing of raw material semicoke particle：Raw material semicoke particle is crushed to the semicoke particle that diameter is not more than 0.5mm；
Detailed process is：Using quartering division sample, first uses jaw crusher moderately broken, is then crushed with ball mill,
Finally the semicoke after crushing is sieved successively with the sieve of 0.5mm, 0.25mm, 0.125mm, 0.074mm, to that cannot penetrate
The semicoke of 0.5mm sieves is further crushed, until ensuring that all samples can be transferred through sieve；
Step 2, the flotation deliming of semicoke particle：The semicoke particle that step 1 obtains is subjected to deliming processing with flotation deliming method,
Obtain flotation deliming semicoke；
Two flotation deliming method of above-mentioned steps is in flotation device rotating speed 1800r/min, aeration quantity 0.21m3It is carried out under conditions of/h,
Detailed process is：
Step（1）, the semicoke particles with water that step 1 is obtained dilutes, and obtains the first slurries, the first concentration of slurry is 60g/L；
Step（2）, surfactant triton x-100 is added in the first slurries, obtains the second slurries；
Step（3）, collecting agent 0 is added in the second slurries#Diesel oil obtains third slurries；
Step（4）, in third slurries be added foaming agent sec-octyl alcohol, obtain upper layer be covered with semicoke bubble and lower layer be impurity
The 4th slurries；
Step（5）, the bubble for being covered with semicoke and impurity of the 4th slurries are detached, the semicoke isolated is taken off again
Water, drying obtain flotation deliming semicoke.
The flotation deliming semicoke that step 2 obtains is carried out deliming processing with chemical deliming method, obtains ultra low-ash by step 3
Divide semicoke；
The detailed process of chemical deliming method in step 3 is：
Step 1, it is first 60 DEG C, a concentration of 6mol/L hydrofluoric acid in temperature by the flotation deliming semicoke that flotation deliming method is handled
In solution, 1.5h is impregnated, is filtered, washing obtains semicoke A；
Step 2, the semicoke A that will be obtained in step 1 impregnates 20min, filtering, water in a concentration of 5mol/L sodium hydroxide solutions
It is washed till filtrate to be in neutrality, suction filtration obtains filter cake, and filter cake is dried；
Step 3, filter cake step 2 obtained is first 60 DEG C, in the hydrochloric acid solution of a concentration of 10mol/L in temperature, impregnates 1h,
It filters, washing obtains semicoke B；
Step 4, the semicoke B that step 3 obtains in a concentration of 5mol/L sodium hydroxide solutions impregnated into 30min, be washed to filtrate
It is in neutrality, suction filtration obtains filter cake, and filter cake is dried, and obtained semicoke content of ashes is 0.17%.
NaF powder is added in the filtrate obtained after the suction filtration of above-mentioned steps 1, then filtrate is heated at a temperature of 360 DEG C
Hydrogen fluoride gas in filtrate can be pyrolyzed out by 2h；The fluorination hydrogen retrieval being pyrolyzed out is got up to recycle.
Specifically reactive mode is：NaF+HF→NaHF2
NaHF2→NaF+HF
Reaction detailed process is above:NaF occurs Chemisorption with the hydrofluoric acid in filtrate first and generates NaHF2, then
Under 360 DEG C of high temperature action, NaHF2It can be pyrolyzed as NaF powder and hydrogen fluoride gas.
Salt is added in the filtrate obtained after the suction filtration of above-mentioned steps 3, then filtrate is distilled, obtains hydrogen chloride gas
Body is recycled.
Embodiment 3：
A kind of preparation method of ultralow ash content semicoke, includes the following steps：
Step 1, the crushing of raw material semicoke particle：Raw material semicoke particle is crushed to the semicoke particle that diameter is not more than 0.5mm；
Detailed process is：Using quartering division sample, first uses jaw crusher moderately broken, is then crushed with ball mill,
Finally the semicoke after crushing is sieved successively with the sieve of 0.5mm, 0.25mm, 0.125mm, 0.074mm, to that cannot penetrate
The semicoke of 0.5mm sieves is further crushed, until ensuring that all samples can be transferred through sieve；
Step 2, the flotation deliming of semicoke particle：The semicoke particle that step 1 obtains is subjected to deliming processing with flotation deliming method,
Obtain flotation deliming semicoke；
Two flotation deliming method of above-mentioned steps is in flotation device rotating speed 1800r/min, aeration quantity 0.21m3It is carried out under conditions of/h,
Detailed process is：
Step（1）, the semicoke particles with water that step 1 is obtained dilutes, and obtains the first slurries, the first concentration of slurry is 60g/L；
Step（2）, surfactant triton x-100 is added in the first slurries, obtains the second slurries；
Step（3）, collecting agent 0 is added in the second slurries#Diesel oil obtains third slurries；
Step（4）, in third slurries be added foaming agent sec-octyl alcohol, obtain upper layer be covered with semicoke bubble and lower layer be impurity
The 4th slurries；
Step（5）, the bubble for being covered with semicoke and impurity of the 4th slurries are detached, the semicoke isolated is taken off again
Water, drying obtain flotation deliming semicoke.
The flotation deliming semicoke that step 2 obtains is carried out deliming processing with chemical deliming method, obtains ultra low-ash by step 3
Divide semicoke；
The detailed process of chemical deliming method in step 3 is：
Step 1, it is first 45 DEG C, a concentration of 4mol/L hydrofluoric acid in temperature by the flotation deliming semicoke that flotation deliming method is handled
In solution, 3h is impregnated, is filtered, washing obtains semicoke particle A；
Step 2, the semicoke A that will be obtained in step 1 impregnates 20min, filtering, water in a concentration of 5mol/L sodium hydroxide solutions
It is washed till filtrate to be in neutrality, suction filtration obtains filter cake, and filter cake is dried；
Step 3, filter cake step 2 obtained is first 40 DEG C, in the hydrochloric acid solution of a concentration of 4mol/L in temperature, impregnates 4h, take out
Filter, washing, obtains semicoke B；
Step 4, the semicoke B that step 3 obtains in a concentration of 5mol/L sodium hydroxide solutions impregnated into 30min, be washed to filtrate
It is in neutrality, suction filtration obtains filter cake, and filter cake is dried, and obtained semicoke content of ashes is 1.04%.
NaF powder is added in the filtrate obtained after the suction filtration of above-mentioned steps 1, then filtrate is heated at a temperature of 360 DEG C
Hydrogen fluoride gas in filtrate can be pyrolyzed out by 2h；The fluorination hydrogen retrieval being pyrolyzed out is got up to recycle.
Specifically reactive mode is：NaF+HF→NaHF2
NaHF2→NaF+HF
Reaction detailed process is above:NaF occurs Chemisorption with the hydrofluoric acid in filtrate first and generates NaHF2, then
Under 360 DEG C of high temperature action, NaHF2It can be pyrolyzed as NaF powder and hydrogen fluoride gas.
Salt is added in the filtrate obtained after the suction filtration of above-mentioned steps 3, then filtrate is distilled, obtains hydrogen chloride gas
Body is recycled.
Embodiment 4：
A kind of preparation method of ultralow ash content semicoke, includes the following steps：
Step 1, the crushing of raw material semicoke particle：Raw material semicoke particle is crushed to the semicoke particle that diameter is not more than 0.5mm；
Detailed process is：Using quartering division sample, first uses jaw crusher moderately broken, is then crushed with ball mill,
Finally the semicoke particle after crushing is sieved successively with the sieve of 0.5mm, 0.25mm, 0.125mm, 0.074mm, to cannot
It is further crushed through the semicoke particle of 0.5mm sieves, until ensuring that all samples can be transferred through sieve；
Step 2, the flotation deliming of semicoke particle：The semicoke particle that step 1 obtains is subjected to deliming processing with flotation deliming method,
Obtain flotation deliming semicoke；
Two flotation deliming method of above-mentioned steps is in flotation device rotating speed 1800r/min, aeration quantity 0.21m3It is carried out under conditions of/h,
Detailed process is：
Step（1）, the semicoke particles with water that step 1 is obtained dilutes, and obtains the first slurries, the first concentration of slurry is 60g/L；
Step（2）, surfactant triton x-100 is added in the first slurries, obtains the second slurries；
Step（3）, collecting agent 0 is added in the second slurries#Diesel oil obtains third slurries；
Step（4）, in third slurries be added foaming agent sec-octyl alcohol, obtain upper layer be covered with semicoke particle bubble and lower layer be
4th slurries of impurity；
Step（5）, the bubble for being covered with semicoke particle and impurity of the 4th slurries are detached, again by the semicoke particle isolated
It is dehydrated, dried, obtain flotation deliming semicoke.
The flotation deliming semicoke that step 2 obtains is carried out deliming processing with chemical deliming method, obtains ultra low-ash by step 3
Divide semicoke；
The detailed process of chemical deliming method in step 3 is：
Step 1, it is first 50 DEG C, a concentration of 4mol/L hydrofluoric acid in temperature by the flotation deliming semicoke that flotation deliming method is handled
In solution, 2h is impregnated, is filtered, washing obtains semicoke particle A；
Step 2, the semicoke particle A that will be obtained in step 1 impregnates 20min, mistake in a concentration of 5mol/L sodium hydroxide solutions
It filters, be washed to filtrate and be in neutrality, suction filtration obtains filter cake, and filter cake is dried；
Step 3, filter cake step 2 obtained is first 50 DEG C, in the hydrochloric acid solution of a concentration of 8mol/L in temperature, it is small to impregnate 2
When, it filters, washing obtains semicoke particle B；
Step 4, the semicoke particle B that step 3 obtains in a concentration of 5mol/L sodium hydroxide solutions impregnated into 30min, be washed to
Filtrate is in neutrality, and suction filtration obtains filter cake, and filter cake is dried, and obtained semicoke particle content of ashes is 0.23%.
NaF powder is added in the filtrate obtained after the suction filtration of above-mentioned steps 1, then filtrate is heated at a temperature of 360 DEG C
Hydrogen fluoride gas in filtrate can be pyrolyzed out by 2h；The fluorination hydrogen retrieval being pyrolyzed out is got up to recycle.
Specifically reactive mode is：NaF+HF→NaHF2
NaHF2→NaF+HF
Reaction detailed process is above:NaF occurs Chemisorption with the hydrofluoric acid in filtrate first and generates NaHF2, then
Under 360 DEG C of high temperature action, NaHF2It can be pyrolyzed as NaF powder and hydrogen fluoride gas.
Salt is added in the filtrate obtained after the suction filtration of above-mentioned steps 3, then filtrate is distilled, obtains hydrogen chloride gas
Body is recycled.
Embodiment 5：
A kind of preparation method of ultralow ash content semicoke particle, includes the following steps：
Step 1, the crushing of raw material semicoke particle：Raw material semicoke is crushed to the semicoke particle that diameter is not more than 0.5mm；Specifically
Process is：Using quartering division sample, first uses jaw crusher moderately broken, then crushed with ball mill, finally
Semicoke after crushing is sieved successively with the sieve of 0.5mm, 0.25mm, 0.125mm, 0.074mm, to that cannot penetrate
The semicoke of 0.5mm sieves is further crushed, until ensuring that all samples can be transferred through sieve；
Step 2, the flotation deliming of semicoke particle：The semicoke particle that step 1 obtains is subjected to deliming processing with flotation deliming method,
Obtain flotation deliming semicoke；
Two flotation deliming method of above-mentioned steps is in flotation device rotating speed 1800r/min, aeration quantity 0.21m3It is carried out under conditions of/h,
Detailed process is：
Step（1）, the semicoke particles with water that step 1 is obtained dilutes, and obtains the first slurries, the first concentration of slurry is 60g/L；
Step（2）, surfactant triton x-100 is added in the first slurries, obtains the second slurries；
Step（3）, collecting agent 0 is added in the second slurries#Diesel oil obtains third slurries；
Step（4）, in third slurries be added foaming agent sec-octyl alcohol, obtain upper layer be covered with semicoke bubble and lower layer be impurity
The 4th slurries；
Step（5）, the bubble for being covered with semicoke and impurity of the 4th slurries are detached, the semicoke isolated is taken off again
Water, drying obtain flotation deliming semicoke.
The flotation deliming semicoke that step 2 obtains is carried out deliming processing with chemical deliming method, obtains ultra low-ash by step 3
Divide semicoke；
The detailed process of chemical deliming method in step 3 is：
Step 1, it is first 55 DEG C, a concentration of 4mol/L hydrofluoric acid in temperature by the flotation deliming semicoke that flotation deliming method is handled
In solution, 2h is impregnated, is filtered, washing obtains semicoke A；
Step 2, the semicoke A that will be obtained in step 1 impregnates 20min, filtering, water in a concentration of 5mol/L sodium hydroxide solutions
It is washed till filtrate to be in neutrality, suction filtration obtains filter cake, and filter cake is dried；
Step 3, filter cake step 2 obtained is first 55 DEG C, in the hydrochloric acid solution of a concentration of 6mol/L in temperature, it is small to impregnate 4
When, it filters, washing obtains semicoke B；
Step 4, the semicoke B that step 3 obtains in a concentration of 5mol/L sodium hydroxide solutions impregnated into 30min, be washed to filtrate
It is in neutrality, suction filtration obtains filter cake, and filter cake is dried, and obtained semicoke content of ashes is 0.52%.
NaF powder is added in the filtrate obtained after the suction filtration of above-mentioned steps 1, then filtrate is heated at a temperature of 360 DEG C
Hydrogen fluoride gas in filtrate can be pyrolyzed out by 2h；The fluorination hydrogen retrieval being pyrolyzed out is got up to recycle.
Specifically reactive mode is：NaF+HF→NaHF2
NaHF2→NaF+HF
Reaction detailed process is above:NaF occurs Chemisorption with the hydrofluoric acid in filtrate first and generates NaHF2, then
Under 360 DEG C of high temperature action, NaHF2It can be pyrolyzed as NaF powder and hydrogen fluoride gas.
Salt is added in the filtrate obtained after the suction filtration of above-mentioned steps 3, then filtrate is distilled, obtains hydrogen chloride gas
Body is recycled.
Embodiment 6：
A kind of preparation method of ultralow ash content semicoke, includes the following steps：
Step 1, the crushing of raw material semicoke particle：Raw material semicoke particle is crushed to the semicoke particle that diameter is not more than 0.5mm；
Detailed process is：Using quartering division sample, first uses jaw crusher moderately broken, is then crushed with ball mill,
Finally the semicoke after crushing is sieved successively with the sieve of 0.5mm, 0.25mm, 0.125mm, 0.074mm, to that cannot penetrate
The semicoke particle of 0.5mm sieves is further crushed, until ensuring that all samples can be transferred through sieve；
Step 2, the flotation deliming of semicoke particle：The semicoke particle that step 1 obtains is subjected to deliming processing with flotation deliming method,
Obtain flotation deliming semicoke；
Two flotation deliming method of above-mentioned steps is in flotation device rotating speed 1800r/min, aeration quantity 0.21m3It is carried out under conditions of/h,
Detailed process is：
Step（1）, the semicoke particles with water that step 1 is obtained dilutes, and obtains the first slurries, the first concentration of slurry is 60g/L；
Step（2）, surfactant triton x-100 is added in the first slurries, obtains the second slurries；
Step（3）, collecting agent 0 is added in the second slurries#Diesel oil obtains third slurries；
Step（4）, in third slurries be added foaming agent sec-octyl alcohol, obtain upper layer be covered with semicoke bubble and lower layer be impurity
The 4th slurries；
Step（5）, the bubble for being covered with semicoke and impurity of the 4th slurries are detached, the semicoke isolated is taken off again
Water, drying obtain flotation deliming semicoke.
The flotation deliming semicoke that step 2 obtains is carried out deliming processing with chemical deliming method, obtains ultra low-ash by step 3
Divide semicoke；
The detailed process of chemical deliming method in step 3 is：
Step 1, it is first 60 DEG C, a concentration of 4mol/L hydrofluoric acid in temperature by the flotation deliming semicoke that flotation deliming method is handled
In solution, 2h is impregnated, is filtered, washing obtains semicoke A；
Step 2, the semicoke A that will be obtained in step 1 impregnates 20min, filtering, water in a concentration of 5mol/L sodium hydroxide solutions
It is washed till filtrate to be in neutrality, suction filtration obtains filter cake, and filter cake is dried；
Step 3, filter cake step 2 obtained is first 60 DEG C, in the hydrochloric acid solution of a concentration of 10mol/L in temperature, it is small to impregnate 2
When, it filters, washing obtains semicoke B；
Step 4, the semicoke B that step 3 obtains in a concentration of 5mol/L sodium hydroxide solutions impregnated into 30min, be washed to filtrate
It is in neutrality, suction filtration obtains filter cake, and filter cake is dried, and obtained semicoke content of ashes is 0.18%.
NaF powder is added in the filtrate obtained after the suction filtration of above-mentioned steps 1, then filtrate is heated at a temperature of 360 DEG C
Hydrogen fluoride gas in filtrate can be pyrolyzed out by 2h；The fluorination hydrogen retrieval being pyrolyzed out is got up to recycle.
Specifically reactive mode is：NaF+HF→NaHF2
NaHF2→NaF+HF
Reaction detailed process is above:NaF occurs Chemisorption with the hydrofluoric acid in filtrate first and generates NaHF2, then
Under 360 DEG C of high temperature action, NaHF2It can be pyrolyzed as NaF powder and hydrogen fluoride gas.
Salt is added in the filtrate obtained after the suction filtration of above-mentioned steps 3, then filtrate is distilled, obtains hydrogen chloride gas
Body is recycled.
It is some detection and analysises made by the ultralow ash content semicoke to the present invention below：
Half-and-half burnt content of ashes has large effect, the present invention to pass through to two kinds of acid concentrations for hydrofluoric acid concentration and concentration of hydrochloric acid variation
It is preferred and reasonably add step, the ultralow semicoke of content of ashes can be prepared.Below to the hydrogen in chemical deliming method
The selection mechanism of fluoric acid and hydrochloric acid illustrates：
Fig. 2 is the semicoke particle content of ashes change curve after hydrofluoric acid treatment, and Fig. 3 contains for semicoke particle ash content after HCl treatment
Measure change curve.
Semicoke particle after flotation deliming is after various concentration hydrofluoric acid treatment, as shown in Figure 2, various concentration hydrofluoric acid pair
The ash content of semicoke particle is affected, and as hydrofluoric acid concentration increases, semicoke particle ash content constantly declines, through 6mol/L hydrofluoric acid
Semicoke particle ash content reduces most after processing, and ash content reaches 1.52%；Before hydrofluoric acid concentration reaches 4mol/L, ash content removing
Rate is larger, and when hydrofluoric acid concentration further increases, ash content although continues to reduce but reduction rate eases up；In view of hydrofluoric acid
Influence of the concentration for environment selects the hydrofluoric acid solution of 4mol/L to carry out deliming experiment；After 4mol/L hydrofluoric acid treatments
Semicoke particle, ash content 1.61% are still relatively high.
The semicoke particle now crossed to a concentration of 4 mol/L hydrofluoric acid treatments continues to be continued with various concentration hydrochloric acid, by
After Fig. 3 is it is found that hydrochloric acid continues with, increase with concentration of hydrochloric acid, ash content persistently reduces；When concentration of hydrochloric acid increases to 8mol/L, half
Burnt particle content of ashes is down to 0.23% hereinafter, preparing ultralow ash content semicoke.
After various concentration hydrofluoric acid is to the processing of semicoke particle deliming, specific content of ashes is shown in Table 1：
1 various concentration hydrofluoric acid of table and its corresponding semicoke particle content of ashes
Semicoke after a concentration of 4 mol/L hydrofluoric acid delimings, then respectively deliming processing, ash content are carried out with the hydrochloric acid of following concentration
Content see the table below 2：
2 various concentration hydrochloric acid of table and its corresponding semicoke particle content of ashes
As shown in Table 2, the ultralow ash content semicoke content of ashes minimum 0.20% prepared.
Fig. 4 is semicoke particle and ultralow ash content semicoke XRD diagram.
As shown in Figure 4, all have in semicoke particle and ultralow ash content semicoke XRD diagram level off to graphite crystal (002) and
(100) the diffractive features peak of crystal face.By being found to diffraction maximum analysis, host inorganic minerals are quartz and side in semicoke particle
Xie Shi can remove the mineral compositions such as silica and the silicate in quartz and calcite through hydrofluoric acid treatment, through hydrochloric acid
Processing can remove the mineral compositions such as carbonate in calcite, so selecting the hydrofluoric acid and reasonable concentration of reasonable concentration successively
Hydrochloric acid respectively to semicoke deliming, deliming effect is significant.It is optimal that ash content can be reduced to 0.20% hereinafter, ultra low-ash is made
Divide semicoke.
Specifically reaction mechanism is：Due to hydrofluoric acid have extremely strong corrosion and permeability, easily with silica and silicic acid
Reactant salt generates Gaseous silicon tetrafluoride, and in ash content is mainly the minerals such as kaolinite, quartz, calcite, these minerals
Ingredient has silica, silicate, carbonate, sulfate etc.；Hydrofluoric acid can be anti-with silica, silicate in minerals etc.
Silicofluoric acid should be generated, then through being decomposed into gaseous ocratation.But the product that hydrofluoric acid is reacted with certain mineral, as calcirm-fluoride,
Ferric flouride etc. is not soluble in water.But these substances dissolve in hydrochloric acid；And hydrochloric acid belongs to strong acid, can make carbonate and major part
Sulfate dissolves, thus can remove the equal carbonate in semicoke particle mineral and the fluoride through hydrofluoric acid dipping generation
It goes.
Here the structure and absorption property of the ultralow ash content semicoke prepared to embodiment 4 are detected and analyzed.
Fig. 5 is semicoke particle and ultralow ash content semicoke N2Adsorption desorption isothermal curve.
As shown in Figure 5, the two N2Adsorption desorption isothermal curve shape distinguishes larger, ultralow ash content semicoke N2Adsorbance compares semicoke
Particle is big.
According to BDDT (Brunauer Deming Deming Teller) adsorption isotherm sorting technique, semicoke particle N2
Adsorption desorption isothermal curve belongs to I type thermoisopleth, its main feature is that low-pressure area large amount of adsorption, with relative pressure (P/Po) increase,
It is little to adsorb increment, forms one close to horizontal platform, desorption curve is not overlapped with adsorption curve, is deposited in semicoke particle
Capillary condensation phenomenon occurs in middle macropore, De contamination isothermal curve is made not to be closed.Ultralow ash content semicoke N2Adsorption desorption isothermal is bent
Line belongs to IV type thermoisopleths.Its main feature is that low-pressure area adsorbance rises rapidly, curve is convex.Thermoisopleth inflection point typically appears in
Near monolayer adsorption, with continuing growing for relative pressure, multilayer absorption gradually forms, but latter section of curve is raised again, and in
Between section be likely to occur absorption hysteresis loop.
Fig. 6 is semicoke particle and ultralow ash content semicoke pore-size distribution situation：
It will be appreciated from fig. 6 that semicoke particle has mesoporous and a small amount of micropore；The micropore and mesopore volume incremental raio of ultralow ash content semicoke half
Burnt particle is high, and the pore-size distribution of ultralow ash content semicoke is more concentrated than semicoke particle.
3 semicoke particle of table and ultralow ash content semicoke pore structure study and absorption property experimental result
Semicoke specific grain surface product is 120.86m known in table 32/ g, total pore volume 0.07cm3/ g, Micropore volume 0.04cm3/ g,
Mesoporous holds 0.03cm3/ g, average pore size 2.61nm, hole have certain development, specific surface area smaller.Reflect semicoke granular absorption
The index of performance, methylene blue value 16mg/g, iodine number 201mg/g are smaller.Illustrate that semicoke granular absorption is indifferent.Through
After crossing deliming processing, the specific surface area of ultralow ash content semicoke is 363.45m2/ g, total pore volume 0.24cm3/ g, Micropore volume
0.13cm3/ g, mesoporous hold 0.10cm3/ g, average pore size 2.32nm, the specific surface area of ultralow ash content semicoke, which has, more significantly to be carried
Height increases 3 times.Total pore volume, micropore volume and mesoporous appearance dramatically increase, and average pore size reduces.Because de- by depth
Ash processing, the intragranular ash content of semicoke react removing with acid, and semicoke particle internal void increases, and specific surface area increases, and aperture becomes
It is small.
Fig. 7 is semicoke particle and ultralow ash content semicoke infrared spectrogram.
As shown in Figure 7, it compares semicoke particle and the ultralow infrared suction of ash content semicoke can be seen in ultralow ash content semicoke infrared spectrum
Receive peak enhancing, especially 3400cm-1Place and in 1800-1300cm-1Wave-number range absorption peak is remarkably reinforced, 3400cm-1It is anti-
Reflect carboxyl ,-OH stretching vibration peaks in phenolic hydroxyl group, 1800-1300cm-1Wave-number range absorption peak reflects C=O stretching vibration features
Peak, C=O and C=C grip superposition absorption peak altogether；O-H bending vibration characteristic peaks, can be attributed to by esters, acid anhydrides, carboxylic acid, lactone, ester
C=O in the functional groups such as class and quinones vibrates the characteristic peak to be formed, and flotation and compound acid system deliming, ultra low-ash are passed through in deducibility
Semicoke surface oxygen functional group is divided to increase, oxygen-containing functional group increases, and absorption property improves.
The analysis of the ultralow ash content semicoke structure and absorption property that are prepared by embodiment 4 is it is found that ultralow ash content semicoke is inhaled
Attached performance significantly improves, along with the ultralow ash content semicoke content of ashes prepared is very low, can by ultralow ash content semicoke into
Ultralow ash content active carbocoal is prepared in row activation, and ultralow ash content active carbocoal is then applied to Absorption Type Blood Detoxifier-Initial
In research, and applied to clinic；And has scientist now and apply the active carbocoal of high adsorption in blood detoxification
Precedent；At that time, the minimum ultralow ash content semicoke of content of ashes will become the optimum feed stock for preparing high adsorption active carbocoal,
This also for future studies first aid detoxification device, absorbent-type artificial kidney, artificial liver critical piece etc. have it is prodigious
It helps.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
The specific implementation of the present invention is confined to these explanations.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to the present invention's
Protection domain.
Claims (9)
1. a kind of preparation method of ultralow ash content semicoke, which is characterized in that this approach includes the following steps：
Step 1, raw material semicoke particle crush：Raw material semicoke particle is crushed to the semicoke particle that diameter is not more than 0.5mm；
Step 2, the flotation deliming of semicoke particle：The semicoke particle that step 1 obtains is subjected to deliming processing with flotation deliming method,
Obtain flotation deliming semicoke；
Step 3, the chemical deliming of semicoke：The flotation deliming semicoke that step 2 obtains is subjected to deliming processing with chemical deliming method,
Obtain ultralow ash content semicoke；
The detailed process of chemical deliming method in the step 3 is：
Step 1, flotation deliming semicoke flotation deliming method handled first temperature be 40 DEG C~60 DEG C, it is a concentration of
In 0.5mol/L~6mol/L hydrofluoric acid solutions, 1.5~3h is impregnated, is then filtered, washed, obtain semicoke A；
Step 2, the semicoke A that will be obtained in step 1 impregnates in a concentration of 5mol/L sodium hydroxide solutions, filters, is washed to filter
Liquid is in neutrality, and suction filtration obtains filter cake, and filter cake is dried；
Step 3, filter cake step 2 obtained is first 40 DEG C~60 DEG C, the hydrochloric acid of a concentration of 4mol/L~10mol/L in temperature
In solution, 1~4h is impregnated, is then filtered, washed, obtain semicoke B；
Step 4, the semicoke B that step 3 obtains impregnated in a concentration of 5mol/L sodium hydroxide solutions, be washed to during filtrate is in
Property, suction filtration obtains filter cake, is dried to filter cake, obtains ultralow ash content semicoke.
2. a kind of preparation method of ultralow ash content semicoke according to claim 1, which is characterized in that floated in the step 2
The detailed process of deliming method is selected to be：
Step（1）, the semicoke particles with water that the step 1 is obtained dilutes, and obtains the first slurries；
Step（2）, surfactant is added in first slurries, obtains the second slurries；
Step（3）, collecting agent is added in second slurries, obtains third slurries；
Step（4）, foaming agent is added in the third slurries, obtain upper layer be covered with semicoke bubble and lower layer be impurity
4th slurries；
Step（5）, the bubble for being covered with semicoke and impurity of the 4th slurries are detached, the semicoke isolated is carried out again
Dehydration, drying, obtain flotation deliming semicoke.
3. a kind of preparation method of ultralow ash content semicoke according to claim 2, which is characterized in that the surfactant
For triton x-100；The collecting agent is 0#Diesel oil；The foaming agent is sec-octyl alcohol.
4. a kind of preparation method of ultralow ash content semicoke according to claim 2, which is characterized in that the flotation deliming method
It is in flotation device rotating speed 1800r/min, aeration quantity 0.21m3It is carried out under conditions of/h.
5. a kind of preparation method of ultralow ash content semicoke according to claim 1, which is characterized in that in the step 2
The time impregnated in sodium hydroxide solution is 20min.
6. a kind of preparation method of ultralow ash content semicoke according to claim 1, which is characterized in that in the step 4
The time impregnated in sodium hydroxide solution is 30min.
7. a kind of preparation method of ultralow ash content semicoke according to claim 1, which is characterized in that the step 1 filters
NaF powder is added in obtained filtrate, is then heated at a temperature of 360 DEG C, recycles hydrogen fluoride.
8. a kind of preparation method of ultralow ash content semicoke according to claim 1, which is characterized in that taken out in the step 3
It filters in obtained filtrate and salt is added, filtrate is distilled, recycle hydrogen chloride.
9. ultralow ash content semicoke prepared by a kind of any one of claim 1~8 the method, which is characterized in that the ultra low-ash
Point semicoke content of ashes is minimum reaches 0.20%.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112919977A (en) * | 2021-04-12 | 2021-06-08 | 兰州交通大学 | Modified oil shale semicoke coated slow and controlled release fertilizer and preparation method thereof |
| CN113088309A (en) * | 2021-03-04 | 2021-07-09 | 唐钢美锦（唐山）煤化工有限公司 | Method and device for reducing ash content in coke powder |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030209495A1 (en) * | 2002-03-12 | 2003-11-13 | Andreas Schlegel | Mixtures of adsorber materials |
| CN106622124A (en) * | 2016-11-29 | 2017-05-10 | 西安科技大学 | High-adsorbability activated semi-coke as well as preparation method and application thereof |
| CN106669601A (en) * | 2016-11-29 | 2017-05-17 | 西安科技大学 | High-absorbability activated semi-coke and preparation method and application thereof |
| CN106733208A (en) * | 2017-01-11 | 2017-05-31 | 青岛海西万润达集团有限公司 | Low ash content semi-coke and its wet flotation technique |
-
2018
- 2018-04-17 CN CN201810340622.7A patent/CN108421530B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20030209495A1 (en) * | 2002-03-12 | 2003-11-13 | Andreas Schlegel | Mixtures of adsorber materials |
| CN106622124A (en) * | 2016-11-29 | 2017-05-10 | 西安科技大学 | High-adsorbability activated semi-coke as well as preparation method and application thereof |
| CN106669601A (en) * | 2016-11-29 | 2017-05-17 | 西安科技大学 | High-absorbability activated semi-coke and preparation method and application thereof |
| CN106733208A (en) * | 2017-01-11 | 2017-05-31 | 青岛海西万润达集团有限公司 | Low ash content semi-coke and its wet flotation technique |
Non-Patent Citations (2)
| Title |
|---|
| 加尔金等著: "《含氟气体的回收和加工》", 31 July 1980, 化学工业出版社 * |
| 张丽: "改性活性半焦吸附剂脱除汽油中硫化物的研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113088309A (en) * | 2021-03-04 | 2021-07-09 | 唐钢美锦（唐山）煤化工有限公司 | Method and device for reducing ash content in coke powder |
| CN112919977A (en) * | 2021-04-12 | 2021-06-08 | 兰州交通大学 | Modified oil shale semicoke coated slow and controlled release fertilizer and preparation method thereof |
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