CN108421530B - Ultralow-ash-content semicoke and preparation method thereof - Google Patents

Ultralow-ash-content semicoke and preparation method thereof Download PDF

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CN108421530B
CN108421530B CN201810340622.7A CN201810340622A CN108421530B CN 108421530 B CN108421530 B CN 108421530B CN 201810340622 A CN201810340622 A CN 201810340622A CN 108421530 B CN108421530 B CN 108421530B
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semicoke
flotation
particles
deashing
slurry
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CN108421530A (en
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刘静
杜美利
李刚
杨建利
陈福欣
樊锦文
蔡雨初
汪晓芹
于远祥
贺成杰
刘雷
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Xian University of Science and Technology
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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
    • 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 semi-coke with ultra-low ash content and a preparation method thereof, which comprises the steps of crushing semi-coke particles as raw materials, performing flotation deashing on the semi-coke particles, and performing chemical deashing on the flotation deashed semi-coke, and comprises the following specific steps: crushing raw material semicoke particles to obtain semicoke particles, deashing the semicoke particles by using a flotation deashing method to obtain flotation deashed semicoke, deashing the flotation deashed semicoke by using hydrofluoric acid, deashing by using hydrochloric acid, performing suction filtration to obtain a filter cake, washing and drying the filter cake to obtain the ultralow-ash semicoke. The ash content of the ultralow-ash semicoke prepared by the method can reach 0.20% at least, and compared with the semicoke, the ultralow-ash semicoke has larger specific surface area and stronger adsorption performance.

Description

Ultralow-ash-content semicoke and preparation method thereof
Technical Field
The invention belongs to the technical field of coal chemical industry, and particularly relates to ultra-low ash content semicoke and a preparation method thereof.
Background
The semicoke is a product of coal pyrolysis at a low temperature (600-700 ℃), has carbon as a main component, can be used as a high-quality carbon source, and is mainly used for civil fuel and power generation. However, the semi-coke ash content is high, so that the semi-coke ash can only be used as fuel or for power generation, the added value is low, and the application is limited. In recent years, many studies have been made at home and abroad on the preparation of active semicoke from semicoke. The active semicoke has wide application, simple production process and good economic value, and develops a new direction for the high added value utilization of the semicoke.
However, the semicoke particles contain high ash content, the main component of the ash content is inorganic mineral substances, and the inorganic mineral substances have great influence on the performance of the active semicoke, so that the application of the active semicoke in the field with strict requirement on the ash content is limited. For example, in the fields of medicines, foods and the like, the requirement on the ash content of active semicoke is high; because medicines and foods are closely related to the health of people, if the ash content of the active carbocoal is higher, the adsorption performance of the active carbocoal is poorer, the adsorption treatment of pollutant particles is incomplete, and the sanitation of the medicines and the foods is reduced; on the contrary, if the ash content of the active semicoke is lower, the adsorption performance is better, the adsorption capacity to pollutant particles is stronger, and the sanitation in the fields of medicine and food can be guaranteed better; of course, the active semicoke can be stored in dry form for medical and food products by utilizing its strong adsorbability as the ash content is lower. For example, the high-ash active semicoke is used for decoloring and deodorizing the Japanese sake, and the inorganic mineral substances in the ash can perform catalytic reaction on ethanol at a certain temperature to form acetaldehyde and CO2The quality of the wine is reduced; in addition, if the iron dissolved in the ash exceeds 0.025%, the iron may react with the cyclic amino acids in the wine to form reddish brown colored substances; not only has no decolorization, but also deepens the color of the wine.
In addition, in the preparation process of the active semicoke, the pore-forming process of the semicoke particles is influenced by inorganic mineral substances in ash, so that the pore development is not facilitated. Wigmans T found: the inorganic mineral substance has great influence on the growth of the pores, promotes the aperture to be enlarged, increases the number of mesopores and macropores, causes the integral specific surface area of the active semicoke to be reduced, and finally causes the integral adsorption capacity of the active semicoke to be reduced.
In recent years, the research of the adsorption type blood detoxification device is being widely developed internationally and has been formally applied to the clinic, and the high-adsorption active semicoke is well applied therein; the semicoke with the lowest ash content is used as the best raw material for preparing the high-adsorbability active semicoke, which is greatly helpful for researching the main parts of emergency detoxification devices, adsorption type artificial kidneys and artificial livers in the future.
The active semicoke with ultralow ash content can be prepared by preparing the semicoke with ultralow ash content and activating the semicoke, so that the reduction of the ash content of the semicoke is vital to the preparation of the active semicoke and the wide application of the active semicoke in the fields of medicines, foods and the like.
The existing application numbers are: 201410421871.0, entitled "chemical deashing method of semicoke", the semicoke is deashed by NaOH and neutralized by single acid, the reaction conditions of the NaOH in the method are strict, and particularly the reaction temperature needs to be 300-450 ℃; the using amount of the sodium hydroxide is very large, and the semicoke particles and the sodium hydroxide react according to the proportion of 1 (1-3), so that the cost is increased; meanwhile, more waste liquid is generated in the preparation process, and the waste of resources is caused without reasonable treatment, and the environment is also polluted.
Application No. 201610063655.2, entitled: a preparation method of ultra-pure active semicoke, wherein the ash content of the prepared semicoke is not more than 4 percent; the activated semicoke is firstly delimed by NaOH and then delimed by hydrochloric acid, and the ash content of the prepared semicoke is lower, so that the semicoke reaches the standard of ultrapure semicoke and can play a certain role in sewage treatment; however, the application range of the semicoke with the purity is narrow, so that the semicoke with the purity is limited, and the semicoke with the purity cannot be applied to a wider range in the fields of medical treatment, food and the like, and particularly, the limitation is more obvious in the research aspect of an adsorption type blood detoxification device; moreover, intermediate products in the preparation process are not recycled, so that resource waste is caused, and environmental protection is not facilitated.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides the ultralow-ash content semicoke and the preparation method thereof, the method has the advantages of high ash removal rate, low requirements on reaction conditions, high recycling rate of intermediate products and low environmental pollution, and the prepared ultralow-ash content semicoke has extremely low ash content, good adsorption performance and wider application range.
The technical problem to be solved by the invention is realized by the following technical scheme:
a method for preparing ultra-low ash content semicoke, the method comprising the steps of:
step one, crushing raw material semi-coke particles: crushing the raw material semi-coke particles into semi-coke particles with the diameter of not more than 0.5 mm;
step two, flotation deashing of semicoke particles: performing deliming treatment on the semicoke particles obtained in the step one by using a flotation deliming method to obtain flotation delimed semicoke;
step three, chemically deashing the semicoke: performing deliming treatment on the flotation deliming semicoke obtained in the step two by using a chemical deliming method to obtain ultralow-ash semicoke;
the chemical deashing method in the third step comprises the following specific processes:
step 1, soaking the flotation deashing semicoke obtained by the treatment of the flotation deashing method in a hydrofluoric acid solution with the temperature of 40-60 ℃ and the concentration of 0.5-6 mol/L for 1.5-3 h, then carrying out suction filtration and washing to obtain semicoke A;
step 2, soaking the semicoke A obtained in the step 1 in a sodium hydroxide solution with the concentration of 5mol/L, filtering, washing with water until the filtrate is neutral, performing suction filtration to obtain a filter cake, and drying the filter cake;
step 3, soaking the filter cake obtained in the step 2 in a hydrochloric acid solution with the temperature of 40-60 ℃ and the concentration of 4-10 mol/L for 1-4 h, then carrying out suction filtration and washing to obtain semicoke B;
and 4, soaking the semicoke B obtained in the step 3 in a sodium hydroxide solution with the concentration of 5mol/L, washing with water until the filtrate is neutral, performing suction filtration to obtain a filter cake, and drying the filter cake to obtain the ultralow-ash-content semicoke.
Preferably, the flotation deashing method in the second step comprises the following specific processes:
step (1), diluting the semicoke particles obtained in the step one with water to obtain first slurry;
adding a surfactant into the first slurry to obtain a second slurry;
adding a collecting agent into the second slurry to obtain third slurry;
adding a foaming agent into the third slurry to obtain fourth slurry with upper layer of bubbles fully distributed with semicoke and lower layer of impurities;
and (5) separating the air bubbles and impurities of the fourth slurry fully distributed with the semicoke, and dehydrating and drying the separated semicoke to obtain the flotation deashing semicoke.
Preferably, the surfactant is triton X-100; the collecting agent is 0#Diesel oil; the foaming agent is secondary octanol.
Preferably, the flotation deashing method is implemented at the rotation speed of a flotation machine of 1800r/min and the aeration quantity of 0.21m3Is carried out under the condition of/h.
Preferably, the soaking time in the sodium hydroxide solution in the step 2 is 20 min;
preferably, the soaking time in the sodium hydroxide solution in the step 4 is 30 min;
preferably, NaF powder is added into the filtrate obtained by suction filtration in the step 1, and then the mixture is heated at the temperature of 360 ℃ to recover hydrogen fluoride.
Preferably, salt is added into the filtrate obtained by suction filtration in the step 3, and the filtrate is distilled to recover hydrogen chloride.
The invention also comprises the ultra-low ash content semi-coke prepared by any one of the methods, wherein the ash content of the ultra-low ash content semi-coke is 0.20 percent at least.
Compared with the prior art, the invention has the beneficial effects that:
1. according to the method, the coke is subjected to deashing treatment by selecting the optimal preparation conditions, firstly, the coke particles are subjected to coarse deashing by a flotation deashing method, then minerals such as kaolinite, quartz, calcite and the like which are difficult to completely remove hydrochloric acid in ash are completely removed by utilizing the extremely strong corrosivity and permeability of hydrofluoric acid, then calcium fluoride, ferric fluoride and the like generated in the deashing process of the hydrofluoric acid are dissolved by utilizing the hydrochloric acid, and simultaneously, carbonate and most of sulfate in the calcite which is not removed by the hydrofluoric acid are dissolved by the hydrochloric acid. The ash content of the prepared semicoke is lower, the semicoke purity is higher, a technical basis is provided for further preparation of active semicoke and better application of the active semicoke, and the method is particularly applied to medical research of food storage, adsorption type blood detoxification and the like.
2. In the process of preparing the ultralow-ash semicoke, the deashing reaction temperature of hydrofluoric acid and hydrochloric acid is between 40 and 60 ℃, and the requirement on reaction conditions is low; and because the semicoke is subjected to flotation deashing to remove part of ash, and then is subjected to deashing by hydrofluoric acid and hydrochloric acid, the consumption of part of acid can be saved.
3. According to the ultra-low ash content semi-coke prepared by the invention, through flotation deashing and deep deashing treatment of the composite strong acid, ash content in semi-coke particles can be almost completely removed, so that internal pores of the semi-coke particles are increased, the specific surface area is increased, the pore diameter is reduced, and the adsorption performance of the semi-coke particles is further enhanced.
4. In the invention, NaF powder is added into the filtrate obtained after the filtration in the step 1, and the NaF and the hydrogen fluoride in the filtrate generate chemical adsorption reaction, and the method specifically comprises the following steps: NaF + HF → NaHF2, and then by heating the filtrate, desorption reaction occurs, specifically: NaHF2→ NaF + HF, and then recover the hydrogen fluoride gas and NaF, and the hydrogen fluoride gas and NaF can be recycled, so that resources can be reasonably and effectively utilized; the pollution of the environment is avoided.
Similarly, salt is added to the filtrate obtained after the suction filtration in step 3 of the present invention, and the filtrate is distilled, whereby hydrogen chloride gas can be recovered and reused.
Drawings
FIG. 1 is a flow diagram of a process for the preparation of ultra low ash semicoke according to the present invention;
FIG. 2 is a graph showing the variation of ash content of semicoke particles after hydrofluoric acid treatment according to the present invention;
FIG. 3 is a graph showing the ash content of the semicoke particles after hydrochloric acid treatment according to the present invention;
FIG. 4 is an XRD pattern of ultra-low ash content char particles and char particles produced in example 4 of the present invention;
FIG. 5 shows the ultra-low ash content semicoke particles and semicoke particle N prepared in example 4 of the present invention2Adsorption and desorption isothermal curves;
FIG. 6 is a plot of the pore size distribution of ultra-low ash semicoke particles and semicoke particles prepared in example 4 of the present invention;
FIG. 7 is an infrared spectrum of ultra-low ash semicoke particles and semicoke prepared in example 4 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1:
a preparation method of ultra-low ash content semi-coke comprises the following steps:
step one, crushing raw material semi-coke particles: crushing the raw material semi-coke particles into semi-coke particles with the diameter of not more than 0.5 mm; the specific process is as follows: the method comprises the following steps of (1) carrying out reduction and division on samples by adopting a quartering method, firstly carrying out moderate crushing by adopting a jaw crusher, then carrying out crushing by using a ball mill, finally screening the crushed semicoke by using sieves with the sizes of 0.5mm, 0.25mm, 0.125mm and 0.074mm in sequence, and further crushing semicoke particles which cannot penetrate through the sieves with the sizes of 0.5mm until all the samples can pass through the sieves;
step two, flotation deashing of semicoke particles: performing deliming treatment on the semicoke particles obtained in the step one by using a flotation deliming method to obtain flotation delimed semicoke;
the second flotation deashing method comprises the steps of rotating the flotation machine at 1800r/min and inflating at 0.21m3The specific process is carried out under the condition of/h and comprises the following steps:
diluting the semicoke particles obtained in the step one with water to obtain first slurry, wherein the concentration of the first slurry is 60 g/L;
step (2), adding surfactant Triton X-100 into the first slurry to obtain second slurry;
adding a collecting agent 0 into the second slurry#Diesel oil to obtain third slurry;
step (4), adding a foaming agent, namely octanol, into the third slurry to obtain fourth slurry with upper layers of bubbles full of semicoke and lower layers of impurities;
and (5) separating the air bubbles and impurities of the fourth slurry fully covered with the semicoke, and dehydrating and drying the separated semicoke to obtain the flotation deashing semicoke.
Step three, performing deliming treatment on the flotation deliming semicoke obtained in the step two by using a chemical deliming method to obtain ultralow-ash semicoke with the ash content of less than 1%;
the chemical deashing method in the third step comprises the following specific processes:
step 1, soaking the flotation deashing semicoke obtained by the treatment of the flotation deashing method in a hydrofluoric acid solution with the temperature of 40 ℃ and the concentration of 0.5mol/L for 3 hours, carrying out suction filtration and washing to obtain semicoke A;
step 2, soaking the semicoke A obtained in the step 1 in a sodium hydroxide solution with the concentration of 5mol/L for 20min, filtering, washing with water until the filtrate is neutral, performing suction filtration to obtain a filter cake, and drying the filter cake;
step 3, firstly soaking the filter cake obtained in the step 2 in a hydrochloric acid solution with the temperature of 40 ℃ and the concentration of 4mol/L for 4 hours, and performing suction filtration and water washing to obtain semicoke B;
and 4, soaking the semicoke B obtained in the step 3 in a sodium hydroxide solution with the concentration of 5mol/L for 30min, washing with water until the filtrate is neutral, performing suction filtration to obtain a filter cake, and drying the filter cake to obtain the semicoke with the ash content of 2.15%.
Adding NaF powder into the filtrate obtained after the suction filtration in the step 1, and then heating the filtrate at the temperature of 360 ℃ for 2 hours to pyrolyze out hydrogen fluoride gas in the filtrate; the hydrogen fluoride thermally decomposed is recovered and reused.
The specific reaction mode is as follows: NaF + HF → NaHF2
NaHF2→NaF+HF
The specific process of the reaction is that NaF firstly generates chemical adsorption reaction with hydrofluoric acid in the filtrate to generate NaHF2Then under the action of high temperature of 360 ℃ and the NaHF2Will be pyrolyzed into NaF powder and hydrogen fluoride gas。
And (3) adding salt into the filtrate obtained after the suction filtration in the step (3), and then distilling the filtrate to obtain hydrogen chloride gas, and recovering the hydrogen chloride gas.
Example 2:
a preparation method of ultra-low ash content semi-coke comprises the following steps:
step one, crushing raw material semi-coke particles: crushing the raw material semi-coke particles into semi-coke particles with the diameter of not more than 0.5 mm; the specific process is as follows: the method comprises the following steps of (1) carrying out reduction and division on samples by adopting a quartering method, firstly carrying out moderate crushing by adopting a jaw crusher, then carrying out crushing by using a ball mill, finally screening the crushed semicoke by using sieves with the sizes of 0.5mm, 0.25mm, 0.125mm and 0.074mm in sequence, and further crushing the semicoke which cannot penetrate through the sieves with the sizes of 0.5mm until all the samples can pass through the sieves;
step two, flotation deashing of semicoke particles: performing deliming treatment on the semicoke particles obtained in the step one by using a flotation deliming method to obtain flotation delimed semicoke;
the second flotation deashing method comprises the steps of rotating the flotation machine at 1800r/min and inflating at 0.21m3The specific process is carried out under the condition of/h and comprises the following steps:
diluting the semicoke particles obtained in the step one with water to obtain first slurry, wherein the concentration of the first slurry is 60 g/L;
step (2), adding surfactant Triton X-100 into the first slurry to obtain second slurry;
adding a collecting agent 0 into the second slurry#Diesel oil to obtain third slurry;
step (4), adding a foaming agent, namely octanol, into the third slurry to obtain fourth slurry with upper layers of bubbles full of semicoke and lower layers of impurities;
and (5) separating the air bubbles and impurities of the fourth slurry fully covered with the semicoke, and dehydrating and drying the separated semicoke to obtain the flotation deashing semicoke.
Step three, performing deliming treatment on the flotation deliming semicoke obtained in the step two by using a chemical deliming method to obtain ultralow-ash-content semicoke;
the chemical deashing method in the third step comprises the following specific processes:
step 1, soaking the flotation deashing semicoke obtained by the treatment of the flotation deashing method in a hydrofluoric acid solution with the temperature of 60 ℃ and the concentration of 6mol/L for 1.5h, performing suction filtration, and washing with water to obtain semicoke A;
step 2, soaking the semicoke A obtained in the step 1 in a sodium hydroxide solution with the concentration of 5mol/L for 20min, filtering, washing with water until the filtrate is neutral, performing suction filtration to obtain a filter cake, and drying the filter cake;
step 3, firstly soaking the filter cake obtained in the step 2 in a hydrochloric acid solution with the temperature of 60 ℃ and the concentration of 10mol/L for 1h, and performing suction filtration and water washing to obtain semicoke B;
and 4, soaking the semicoke B obtained in the step 3 in a sodium hydroxide solution with the concentration of 5mol/L for 30min, washing with water until the filtrate is neutral, performing suction filtration to obtain a filter cake, and drying the filter cake to obtain the semicoke with the ash content of 0.17%.
Adding NaF powder into the filtrate obtained after the suction filtration in the step 1, and then heating the filtrate at the temperature of 360 ℃ for 2 hours to pyrolyze out hydrogen fluoride gas in the filtrate; the hydrogen fluoride thermally decomposed is recovered and reused.
The specific reaction mode is as follows: NaF + HF → NaHF2
NaHF2→NaF+HF
The specific process of the reaction is that NaF firstly generates chemical adsorption reaction with hydrofluoric acid in the filtrate to generate NaHF2Then under the action of high temperature of 360 ℃ and the NaHF2It is pyrolyzed into NaF powder and hydrogen fluoride gas.
And (3) adding salt into the filtrate obtained after the suction filtration in the step (3), and then distilling the filtrate to obtain hydrogen chloride gas, and recovering the hydrogen chloride gas.
Example 3:
a preparation method of ultra-low ash content semi-coke comprises the following steps:
step one, crushing raw material semi-coke particles: crushing the raw material semi-coke particles into semi-coke particles with the diameter of not more than 0.5 mm; the specific process is as follows: the method comprises the following steps of (1) carrying out reduction and division on samples by adopting a quartering method, firstly carrying out moderate crushing by adopting a jaw crusher, then carrying out crushing by using a ball mill, finally screening the crushed semicoke by using sieves with the sizes of 0.5mm, 0.25mm, 0.125mm and 0.074mm in sequence, and further crushing the semicoke which cannot penetrate through the sieves with the sizes of 0.5mm until all the samples can pass through the sieves;
step two, flotation deashing of semicoke particles: performing deliming treatment on the semicoke particles obtained in the step one by using a flotation deliming method to obtain flotation delimed semicoke;
the second flotation deashing method comprises the steps of rotating the flotation machine at 1800r/min and inflating at 0.21m3The specific process is carried out under the condition of/h and comprises the following steps:
diluting the semicoke particles obtained in the step one with water to obtain first slurry, wherein the concentration of the first slurry is 60 g/L;
step (2), adding surfactant Triton X-100 into the first slurry to obtain second slurry;
adding a collecting agent 0 into the second slurry#Diesel oil to obtain third slurry;
step (4), adding a foaming agent, namely octanol, into the third slurry to obtain fourth slurry with upper layers of bubbles full of semicoke and lower layers of impurities;
and (5) separating the air bubbles and impurities of the fourth slurry fully covered with the semicoke, and dehydrating and drying the separated semicoke to obtain the flotation deashing semicoke.
Step three, performing deliming treatment on the flotation deliming semicoke obtained in the step two by using a chemical deliming method to obtain ultralow-ash-content semicoke;
the chemical deashing method in the third step comprises the following specific processes:
step 1, soaking the flotation deashing semicoke obtained by the treatment of the flotation deashing method in a hydrofluoric acid solution with the temperature of 45 ℃ and the concentration of 4mol/L for 3 hours, and performing suction filtration and water washing to obtain semicoke particles A;
step 2, soaking the semicoke A obtained in the step 1 in a sodium hydroxide solution with the concentration of 5mol/L for 20min, filtering, washing with water until the filtrate is neutral, performing suction filtration to obtain a filter cake, and drying the filter cake;
step 3, firstly soaking the filter cake obtained in the step 2 in a hydrochloric acid solution with the temperature of 40 ℃ and the concentration of 4mol/L for 4 hours, and performing suction filtration and water washing to obtain semicoke B;
and 4, soaking the semicoke B obtained in the step 3 in a sodium hydroxide solution with the concentration of 5mol/L for 30min, washing with water until the filtrate is neutral, performing suction filtration to obtain a filter cake, and drying the filter cake to obtain the semicoke with the ash content of 1.04%.
Adding NaF powder into the filtrate obtained after the suction filtration in the step 1, and then heating the filtrate at the temperature of 360 ℃ for 2 hours to pyrolyze out hydrogen fluoride gas in the filtrate; the hydrogen fluoride thermally decomposed is recovered and reused.
The specific reaction mode is as follows: NaF + HF → NaHF2
NaHF2→NaF+HF
The specific process of the reaction is that NaF firstly generates chemical adsorption reaction with hydrofluoric acid in the filtrate to generate NaHF2Then under the action of high temperature of 360 ℃ and the NaHF2It is pyrolyzed into NaF powder and hydrogen fluoride gas.
And (3) adding salt into the filtrate obtained after the suction filtration in the step (3), and then distilling the filtrate to obtain hydrogen chloride gas, and recovering the hydrogen chloride gas.
Example 4:
a preparation method of ultra-low ash content semi-coke comprises the following steps:
step one, crushing raw material semi-coke particles: crushing the raw material semi-coke particles into semi-coke particles with the diameter of not more than 0.5 mm; the specific process is as follows: the method comprises the following steps of (1) carrying out reduction and division on a sample by adopting a quartering method, firstly carrying out moderate crushing by adopting a jaw crusher, then carrying out crushing by using a ball mill, finally screening the crushed semicoke particles in turn by using sieves of 0.5mm, 0.25mm, 0.125mm and 0.074mm, and further crushing the semicoke particles which cannot penetrate through the sieves of 0.5mm until all the samples can pass through the sieves;
step two, flotation deashing of semicoke particles: performing deliming treatment on the semicoke particles obtained in the step one by using a flotation deliming method to obtain flotation delimed semicoke;
the second flotation deashing method is that the rotation speed of the flotation machine is 180 DEG0r/min and 0.21m of aeration quantity3The specific process is carried out under the condition of/h and comprises the following steps:
diluting the semicoke particles obtained in the step one with water to obtain first slurry, wherein the concentration of the first slurry is 60 g/L;
step (2), adding surfactant Triton X-100 into the first slurry to obtain second slurry;
adding a collecting agent 0 into the second slurry#Diesel oil to obtain third slurry;
step (4), adding a foaming agent, namely octanol, into the third slurry to obtain fourth slurry with upper layers of bubbles full of semi-coke particles and lower layers of impurities;
and (5) separating the bubbles and impurities of the fourth slurry fully distributed with the semi-coke particles, and dehydrating and drying the separated semi-coke particles to obtain the flotation deashing semi-coke.
Step three, performing deliming treatment on the flotation deliming semicoke obtained in the step two by using a chemical deliming method to obtain ultralow-ash-content semicoke;
the chemical deashing method in the third step comprises the following specific processes:
step 1, soaking the flotation deashing semicoke treated by the flotation deashing method in a hydrofluoric acid solution with the temperature of 50 ℃ and the concentration of 4mol/L for 2 hours, performing suction filtration and washing to obtain semicoke particles A;
step 2, soaking the semicoke particles A obtained in the step 1 in a sodium hydroxide solution with the concentration of 5mol/L for 20min, filtering, washing with water until the filtrate is neutral, performing suction filtration to obtain a filter cake, and drying the filter cake;
step 3, firstly soaking the filter cake obtained in the step 2 in a hydrochloric acid solution with the temperature of 50 ℃ and the concentration of 8mol/L for 2 hours, and performing suction filtration and water washing to obtain semicoke particles B;
and 4, soaking the semicoke particles B obtained in the step 3 in a sodium hydroxide solution with the concentration of 5mol/L for 30min, washing with water until the filtrate is neutral, performing suction filtration to obtain a filter cake, and drying the filter cake to obtain the semicoke particles with the ash content of 0.23%.
Adding NaF powder into the filtrate obtained after the suction filtration in the step 1, and then heating the filtrate at the temperature of 360 ℃ for 2 hours to pyrolyze out hydrogen fluoride gas in the filtrate; the hydrogen fluoride thermally decomposed is recovered and reused.
The specific reaction mode is as follows: NaF + HF → NaHF2
NaHF2→NaF+HF
The specific process of the reaction is that NaF firstly generates chemical adsorption reaction with hydrofluoric acid in the filtrate to generate NaHF2Then under the action of high temperature of 360 ℃ and the NaHF2It is pyrolyzed into NaF powder and hydrogen fluoride gas.
And (3) adding salt into the filtrate obtained after the suction filtration in the step (3), and then distilling the filtrate to obtain hydrogen chloride gas, and recovering the hydrogen chloride gas.
Example 5:
a preparation method of ultra-low ash content semi-coke particles comprises the following steps:
step one, crushing raw material semi-coke particles: crushing the raw material semi-coke into semi-coke particles with the diameter of not more than 0.5 mm; the specific process is as follows: the method comprises the following steps of (1) carrying out reduction and division on samples by adopting a quartering method, firstly carrying out moderate crushing by adopting a jaw crusher, then carrying out crushing by using a ball mill, finally screening the crushed semicoke by using sieves with the sizes of 0.5mm, 0.25mm, 0.125mm and 0.074mm in sequence, and further crushing the semicoke which cannot penetrate through the sieves with the sizes of 0.5mm until all the samples can pass through the sieves;
step two, flotation deashing of semicoke particles: performing deliming treatment on the semicoke particles obtained in the step one by using a flotation deliming method to obtain flotation delimed semicoke;
the second flotation deashing method comprises the steps of rotating the flotation machine at 1800r/min and inflating at 0.21m3The specific process is carried out under the condition of/h and comprises the following steps:
diluting the semicoke particles obtained in the step one with water to obtain first slurry, wherein the concentration of the first slurry is 60 g/L;
step (2), adding surfactant Triton X-100 into the first slurry to obtain second slurry;
adding a collecting agent 0 into the second slurry#Diesel oil to obtain the thirdSlurry;
step (4), adding a foaming agent, namely octanol, into the third slurry to obtain fourth slurry with upper layers of bubbles full of semicoke and lower layers of impurities;
and (5) separating the air bubbles and impurities of the fourth slurry fully covered with the semicoke, and dehydrating and drying the separated semicoke to obtain the flotation deashing semicoke.
Step three, performing deliming treatment on the flotation deliming semicoke obtained in the step two by using a chemical deliming method to obtain ultralow-ash-content semicoke;
the chemical deashing method in the third step comprises the following specific processes:
step 1, soaking the flotation deashing semicoke obtained by the treatment of the flotation deashing method in a hydrofluoric acid solution with the temperature of 55 ℃ and the concentration of 4mol/L for 2 hours, performing suction filtration, and washing with water to obtain semicoke A;
step 2, soaking the semicoke A obtained in the step 1 in a sodium hydroxide solution with the concentration of 5mol/L for 20min, filtering, washing with water until the filtrate is neutral, performing suction filtration to obtain a filter cake, and drying the filter cake;
step 3, firstly soaking the filter cake obtained in the step 2 in a hydrochloric acid solution with the temperature of 55 ℃ and the concentration of 6mol/L for 4 hours, and performing suction filtration and water washing to obtain semicoke B;
and 4, soaking the semicoke B obtained in the step 3 in a sodium hydroxide solution with the concentration of 5mol/L for 30min, washing with water until the filtrate is neutral, performing suction filtration to obtain a filter cake, and drying the filter cake to obtain the semicoke with the ash content of 0.52%.
Adding NaF powder into the filtrate obtained after the suction filtration in the step 1, and then heating the filtrate at the temperature of 360 ℃ for 2 hours to pyrolyze out hydrogen fluoride gas in the filtrate; the hydrogen fluoride thermally decomposed is recovered and reused.
The specific reaction mode is as follows: NaF + HF → NaHF2
NaHF2→NaF+HF
The specific process of the reaction is that NaF firstly generates chemical adsorption reaction with hydrofluoric acid in the filtrate to generate NaHF2Then under the action of high temperature of 360 ℃ and the NaHF2Will pyrolyze into NaF powder and fluorineA hydrogen-oxide gas.
And (3) adding salt into the filtrate obtained after the suction filtration in the step (3), and then distilling the filtrate to obtain hydrogen chloride gas, and recovering the hydrogen chloride gas.
Example 6:
a preparation method of ultra-low ash content semi-coke comprises the following steps:
step one, crushing raw material semi-coke particles: crushing the raw material semi-coke particles into semi-coke particles with the diameter of not more than 0.5 mm; the specific process is as follows: the method comprises the following steps of (1) carrying out reduction and division on samples by adopting a quartering method, firstly carrying out moderate crushing by adopting a jaw crusher, then carrying out crushing by using a ball mill, finally screening the crushed semicoke by using sieves with the sizes of 0.5mm, 0.25mm, 0.125mm and 0.074mm in sequence, and further crushing semicoke particles which cannot penetrate through the sieves with the sizes of 0.5mm until all the samples can pass through the sieves;
step two, flotation deashing of semicoke particles: performing deliming treatment on the semicoke particles obtained in the step one by using a flotation deliming method to obtain flotation delimed semicoke;
the second flotation deashing method comprises the steps of rotating the flotation machine at 1800r/min and inflating at 0.21m3The specific process is carried out under the condition of/h and comprises the following steps:
diluting the semicoke particles obtained in the step one with water to obtain first slurry, wherein the concentration of the first slurry is 60 g/L;
step (2), adding surfactant Triton X-100 into the first slurry to obtain second slurry;
adding a collecting agent 0 into the second slurry#Diesel oil to obtain third slurry;
step (4), adding a foaming agent, namely octanol, into the third slurry to obtain fourth slurry with upper layers of bubbles full of semicoke and lower layers of impurities;
and (5) separating the air bubbles and impurities of the fourth slurry fully covered with the semicoke, and dehydrating and drying the separated semicoke to obtain the flotation deashing semicoke.
Step three, performing deliming treatment on the flotation deliming semicoke obtained in the step two by using a chemical deliming method to obtain ultralow-ash-content semicoke;
the chemical deashing method in the third step comprises the following specific processes:
step 1, soaking the flotation deashing semicoke obtained by the treatment of the flotation deashing method in a hydrofluoric acid solution with the temperature of 60 ℃ and the concentration of 4mol/L for 2 hours, performing suction filtration, and washing with water to obtain semicoke A;
step 2, soaking the semicoke A obtained in the step 1 in a sodium hydroxide solution with the concentration of 5mol/L for 20min, filtering, washing with water until the filtrate is neutral, performing suction filtration to obtain a filter cake, and drying the filter cake;
step 3, firstly soaking the filter cake obtained in the step 2 in a hydrochloric acid solution with the temperature of 60 ℃ and the concentration of 10mol/L for 2 hours, and performing suction filtration and water washing to obtain semicoke B;
and 4, soaking the semicoke B obtained in the step 3 in a sodium hydroxide solution with the concentration of 5mol/L for 30min, washing with water until the filtrate is neutral, performing suction filtration to obtain a filter cake, and drying the filter cake to obtain the semicoke with the ash content of 0.18%.
Adding NaF powder into the filtrate obtained after the suction filtration in the step 1, and then heating the filtrate at the temperature of 360 ℃ for 2 hours to pyrolyze out hydrogen fluoride gas in the filtrate; the hydrogen fluoride thermally decomposed is recovered and reused.
The specific reaction mode is as follows: NaF + HF → NaHF2
NaHF2→NaF+HF
The specific process of the reaction is that NaF firstly generates chemical adsorption reaction with hydrofluoric acid in the filtrate to generate NaHF2Then under the action of high temperature of 360 ℃ and the NaHF2It is pyrolyzed into NaF powder and hydrogen fluoride gas.
And (3) adding salt into the filtrate obtained after the suction filtration in the step (3), and then distilling the filtrate to obtain hydrogen chloride gas, and recovering the hydrogen chloride gas.
The following are some tests and analyses performed on the ultra-low ash semicoke of the present invention:
the concentration change of hydrofluoric acid and hydrochloric acid has great influence on the content of semi-coke ash, and the semi-coke with ultralow ash content can be prepared by optimizing the concentration of the two acids and reasonably adding the two acids. The following is a description of the mechanism of choice of hydrofluoric acid and hydrochloric acid in chemical deliming:
FIG. 2 is a curve showing the ash content of the semicoke particles after hydrofluoric acid treatment, and FIG. 3 is a curve showing the ash content of the semicoke particles after hydrochloric acid treatment.
After the semi-coke particles subjected to flotation and deashing are treated by hydrofluoric acid with different concentrations, as can be seen from fig. 2, the ash content of the semi-coke particles is greatly influenced by hydrofluoric acid with different concentrations, the ash content of the semi-coke particles is continuously reduced along with the increase of the concentration of the hydrofluoric acid, the ash content of the semi-coke particles is reduced most after the semi-coke particles are treated by hydrofluoric acid with concentration of 6mol/L, and the ash content reaches 1.52%; before the concentration of hydrofluoric acid reaches 4mol/L, the ash removal rate is higher, and when the concentration of hydrofluoric acid is further increased, the ash content continues to decrease but the decrease rate is slowed down; considering the influence of the concentration of hydrofluoric acid on the environment, a 4mol/L hydrofluoric acid solution is selected for deliming experiments; the ash content of the semi-coke particles treated by 4mol/L of hydrofluoric acid is 1.61 percent, and is still higher.
At present, the semicoke particles treated by hydrofluoric acid with the concentration of 4mol/L are continuously treated by hydrochloric acid with different concentrations, and as can be seen from figure 3, the ash content is continuously reduced along with the increase of the concentration of the hydrochloric acid after the hydrochloric acid is continuously treated; when the concentration of hydrochloric acid is increased to 8mol/L, the ash content of the semicoke particles is reduced to be below 0.23 percent, and the ultralow-ash semicoke is prepared.
After the semi-coke particles are deashed by hydrofluoric acid with different concentrations, the specific ash content is shown in table 1:
TABLE 1 hydrofluoric acid of different concentrations and corresponding ash content of semicoke particles
Figure DEST_PATH_IMAGE002
The semi-coke after deliming by hydrofluoric acid with the concentration of 4mol/L is delimed by hydrochloric acid with the following concentrations, and the ash content is shown in the following table 2:
TABLE 2 hydrochloric acid of different concentrations and corresponding ash content of semicoke particles
Figure DEST_PATH_IMAGE004
As can be seen from Table 2, the minimum ash content of the ultra-low ash semicoke produced is 0.20%.
Figure 4 is an XRD pattern of the char particles and ultra-low ash content char.
As can be seen from FIG. 4, the XRD patterns of the semicoke particles and the ultra-low ash semicoke have characteristic diffraction peaks approaching to the (002) and (100) crystal planes of graphite crystals. The diffraction peak analysis shows that the main inorganic mineral substances in the semi-coke particles are quartz and calcite, the mineral substances such as silicon dioxide, silicate and the like in the quartz and calcite can be removed by hydrofluoric acid treatment, and the mineral substances such as carbonate and the like in the calcite can be removed by hydrochloric acid treatment, so that the semi-coke is de-ashed by sequentially selecting hydrofluoric acid with reasonable concentration and hydrochloric acid with reasonable concentration, and the de-ashing effect is obvious. The ash content can be optimally reduced to be below 0.20 percent, and the ultra-low ash content semi-coke is prepared.
The specific reaction mechanism is as follows: hydrofluoric acid has strong corrosion and permeability, and is easy to react with silicon dioxide and silicate to generate gaseous silicon tetrafluoride, mineral substances such as kaolinite, quartz, calcite and the like are mainly contained in ash, and the mineral substances comprise silicon dioxide, silicate, carbonate, sulfate and the like; hydrofluoric acid can react with silicon dioxide, silicate and the like in mineral substances to generate silicofluoric acid, and then the silicofluoric acid is decomposed into gaseous silicon tetrafluoride. However, the products of the reaction of hydrofluoric acid with certain minerals, such as calcium fluoride, ferric fluoride, etc., are insoluble in water. But these materials are soluble in hydrochloric acid; since hydrochloric acid is a strong acid and can dissolve carbonate and most of sulfate, the carbonate in the mineral in the semicoke particles and the fluoride generated by hydrofluoric acid impregnation can be removed.
The structure and adsorption performance of the ultra-low ash semicoke prepared in example 4 was examined and analyzed here.
FIG. 5 is a graph of semicoke particles and ultra low ash semicoke N2Adsorption and desorption isotherms.
As can be seen from FIG. 5, both N2The shapes of adsorption and desorption isothermal curves are greatly different, and the semi-coke N with ultralow ash content2The adsorption capacity is larger than that of the semicoke particles.
According to BDDT: (Brunauer Deming Teller) adsorption isotherm classification method, and semicoke particles N2The adsorption-desorption isotherm curve belongs to a type I isotherm and is characterized in that the adsorption capacity of a low-pressure area is large along with the relative pressure (P/P)o) The desorption curve is not superposed with the adsorption curve, and the mesopores in the semicoke particles generate a capillary condensation phenomenon, so that the desorption isothermal curve is not closed. Ultra low ash content semicoke N2The adsorption and desorption isotherm curve belongs to the type IV isotherm. Its advantages are high adsorption capacity in low-pressure region and high convex curve. The inflection point of the isotherm usually occurs near the monolayer adsorption, with the multilayer adsorption developing as the relative pressure continues to increase, but the latter segment of the curve bulges again and the middle segment may show adsorption hysteresis loop.
FIG. 6 shows the pore size distribution of the semicoke particles and the ultralow ash content semicoke:
as can be seen from fig. 6, the semicoke particles had mesopores and a small number of micropores; the micropore volume increment and the mesopore volume increment of the ultra-low ash content semi-coke are higher than those of semi-coke particles, and the pore size distribution of the ultra-low ash content semi-coke is more concentrated than that of the semi-coke particles.
TABLE 3 analysis of the pore structure of the semicoke particles and the ultra-low ash content semicoke and the results of the adsorption performance test
Figure DEST_PATH_IMAGE006
From Table 3, it can be seen that the specific surface area of the semicoke particles is 120.86m2G, total pore volume 0.07cm3Per g, micropore volume of 0.04cm3G, mesopore volume 0.03cm3The volume ratio of the particles is/g, the average pore diameter is 2.61nm, pores develop to a certain extent, and the specific surface area is smaller. The indexes of the absorption performance of the semicoke particles are reflected, and the methylene blue value is 16mg/g, and the iodine value is 201mg/g, which are both smaller. The adsorption capacity of the semicoke particles is not strong. After deashing treatment, the specific surface area of the ultra-low ash content semicoke is 363.45m2G, total pore volume 0.24cm3G, micropore volume of 0.13cm3G, mesopore volume 0.10cm3The specific surface area of the ultralow ash content semicoke is obviously improved and increased by 3 times. The total pore volume, the micro pore volume and the meso pore volume are all obviously increased, and the average pore diameter is reduced. Because of the deep deashing treatment, the ash in the semicoke particles is removed by the reaction with acid, the internal pores of the semicoke particles are increased, the specific surface area is increased, and the pore diameter is reduced.
FIG. 7 is an infrared spectrum of char particles and ultra low ash char.
As can be seen from FIG. 7, the infrared absorption peaks of the ultra-low ash content semicoke are enhanced by comparing the infrared spectra of the semicoke particles and the ultra-low ash content semicoke, particularly 3400cm-1At 1800 and 1300cm-1The absorption peak in the wave number range is obviously enhanced and is 3400cm-1Is a 1300cm of 1800--1Wave number range absorption peaks reflect C = O stretching vibration characteristic peaks, and C = O and C = C conjugate superposition absorption peaks; the characteristic peak of O-H bending vibration can be attributed to the characteristic peak formed by C = O vibration in functional groups such as esters, acid anhydrides, carboxylic acids, lactones, esters, quinones and the like, and the characteristic peak can be inferred that the oxygen-containing functional groups on the surface of the ultra-low ash semi-coke are increased and the oxygen-containing functional groups are increased after flotation and composite acid system deashing, so that the adsorption performance of the ultra-low ash semi-coke is improved.
According to analysis of the structure and the adsorption performance of the ultralow-ash content semicoke prepared in the embodiment 4, the adsorption performance of the ultralow-ash content semicoke is obviously improved, and in addition, the ash content of the prepared ultralow-ash content semicoke is very low, the ultralow-ash content semicoke can be activated to prepare the ultralow-ash content active semicoke, and then the ultralow-ash content active semicoke is applied to research of an adsorption type blood detoxification device and is clinically applied; and scientists have precedent to apply the high-adsorbability active carbocoal in blood detoxification; at that time, the ultralow-ash semicoke with the lowest ash content can become the best raw material for preparing the high-adsorbability active semicoke, which is also greatly helpful for researching the main components of emergency detoxication devices, adsorption type artificial kidneys and artificial livers in the future.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.

Claims (4)

1. A preparation method of ultra-low ash content semi-coke is characterized in that,
the ash content of the ultra-low ash content semi-coke is 0.23%;
the method comprises the following steps:
step one, crushing raw material semi-coke particles: crushing the raw material semi-coke particles into semi-coke particles with the diameter of not more than 0.5 mm;
step two, flotation deashing of semicoke particles: performing deliming treatment on the semicoke particles obtained in the step one by using a flotation deliming method to obtain flotation delimed semicoke;
step three, chemically deashing the semicoke: performing deliming treatment on the flotation deliming semicoke obtained in the step two by using a chemical deliming method to obtain ultralow-ash semicoke;
the chemical deashing method in the third step comprises the following specific processes:
step 1, soaking the flotation deashing semicoke treated by the flotation deashing method in a hydrofluoric acid solution with the temperature of 50 ℃ and the concentration of 4mol/L for 2 hours, performing suction filtration and washing to obtain semicoke particles A;
step 2, soaking the semicoke particles A obtained in the step 1 in a sodium hydroxide solution with the concentration of 5mol/L for 20min, filtering, washing with water until the filtrate is neutral, performing suction filtration to obtain a filter cake, and drying the filter cake;
step 3, firstly soaking the filter cake obtained in the step 2 in a hydrochloric acid solution with the temperature of 50 ℃ and the concentration of 8mol/L for 2 hours, and performing suction filtration and water washing to obtain semicoke particles B;
step 4, soaking the semicoke particles B obtained in the step 3 in a sodium hydroxide solution with the concentration of 5mol/L for 30min, washing with water until the filtrate is neutral, performing suction filtration to obtain a filter cake, and drying the filter cake to obtain the ultralow-ash semicoke;
adding NaF powder into the filtrate obtained by suction filtration in the step 1, heating at the temperature of 360 ℃, and recovering hydrogen fluoride;
and (3) adding salt into the filtrate obtained by suction filtration in the step (3), distilling the filtrate, and recovering hydrogen chloride.
2. The method for preparing the ultra-low ash content semi-coke according to claim 1, wherein the flotation deashing method in the second step comprises the following specific processes:
step (1), diluting the semicoke particles obtained in the step one with water to obtain first slurry;
adding a surfactant into the first slurry to obtain a second slurry;
adding a collecting agent into the second slurry to obtain third slurry;
adding a foaming agent into the third slurry to obtain fourth slurry with upper layer of bubbles fully distributed with semicoke and lower layer of impurities;
and (5) separating the air bubbles and impurities of the fourth slurry fully distributed with the semicoke, and dehydrating and drying the separated semicoke to obtain the flotation deashing semicoke.
3. The method for preparing the ultra-low ash content semicoke according to claim 2, wherein the surfactant is triton X-100; the collecting agent is 0#Diesel oil; the foaming agent is secondary octanol.
4. The method for preparing the ultra-low ash content semicoke according to claim 2, wherein the flotation deashing method is carried out at a rotation speed of a flotation machine of 1800r/min and an aeration quantity of 0.21m3Is carried out under the condition of/h.
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