CN106395816B - A method of residue prepares adsorbent after extracting humic acid by lignite - Google Patents
A method of residue prepares adsorbent after extracting humic acid by lignite Download PDFInfo
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- CN106395816B CN106395816B CN201610800830.1A CN201610800830A CN106395816B CN 106395816 B CN106395816 B CN 106395816B CN 201610800830 A CN201610800830 A CN 201610800830A CN 106395816 B CN106395816 B CN 106395816B
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- 239000003077 lignite Substances 0.000 title claims abstract description 49
- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000004021 humic acid Substances 0.000 title claims abstract description 38
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000003463 adsorbent Substances 0.000 title claims abstract description 22
- 238000000197 pyrolysis Methods 0.000 claims abstract description 42
- 239000007789 gas Substances 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 238000001816 cooling Methods 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 5
- 238000010521 absorption reaction Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000009833 condensation Methods 0.000 claims abstract description 3
- 230000005494 condensation Effects 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 26
- 239000002817 coal dust Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000008236 heating water Substances 0.000 claims description 6
- 239000013049 sediment Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 235000019476 oil-water mixture Nutrition 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000005520 cutting process Methods 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 230000000630 rising effect Effects 0.000 claims 1
- 239000003245 coal Substances 0.000 abstract description 25
- 239000003513 alkali Substances 0.000 abstract description 19
- 230000008569 process Effects 0.000 abstract description 13
- 230000004913 activation Effects 0.000 abstract description 9
- 239000012265 solid product Substances 0.000 abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 8
- 239000006227 byproduct Substances 0.000 abstract description 7
- 238000004458 analytical method Methods 0.000 abstract description 5
- 230000004048 modification Effects 0.000 abstract description 2
- 238000012986 modification Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000000463 material Substances 0.000 abstract 1
- 239000011269 tar Substances 0.000 description 10
- 238000001994 activation Methods 0.000 description 9
- 239000000571 coke Substances 0.000 description 9
- 239000000126 substance Substances 0.000 description 8
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 229910052740 iodine Inorganic materials 0.000 description 6
- 239000011630 iodine Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 235000019198 oils Nutrition 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000011148 porous material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000000605 extraction Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000000284 extract Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 239000002154 agricultural waste Substances 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000003610 charcoal Substances 0.000 description 2
- 239000003034 coal gas Substances 0.000 description 2
- 239000011280 coal tar Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000012216 screening Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 1
- 239000012190 activator Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000004519 grease Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003786 synthesis reaction 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
- 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
- B01J2220/4875—Sorbents characterised by the starting material used for their preparation the starting material being a waste, residue or of undefined composition
- B01J2220/4887—Residues, wastes, e.g. garbage, municipal or industrial sludges, compost, animal manure; fly-ashes
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
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- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses the methods that residue after a kind of extracting humic acid by lignite prepares adsorbent, Lignitic Humic Acid is extracted using alkali-soluble acid analysis method, residue is pyrolyzed at 760~940 DEG C, tar and hydrogen-rich gas are produced in the condensation cooling of pyrolysis gas product, pyrolysis solid product washing drying prepares carbonaceous adsorbent, and the staged conversion for realizing lignite utilizes.Lye after the method for the present invention is extracted using coal humic acid in residue, one-step method high temperature pyrolysis prepares the carbonaceous adsorbent that specific surface area is high, absorption property is good, overcome traditional alkali activation method prepare alkali charge in activated carbon process big, complex process, problem at high cost.The tar of by-product contains that pyrolysis water is few, and separation is easy, and tar yield is high, and the raw gas of by-product has very high H2With CO content, CH4Content is low, is highly suitable as material gas after producing the purified modification of gas.
Description
Technical field
The present invention relates to a kind of coal comprehensive utilization technique, after specifically a kind of extracting humic acid by coal prepared by residue
The method of adsorbent.
Background technique
With a large amount of exploitations of coal, China's high-quality coal resource is gradually decreased, but the abundant underutilization of lignite resource,
The lignite resource of rich reserves be efficiently worth using with very high economy and society.Therefore, lignite is effectively improved
It comprehensively utilizes and develops towards high value added product direction and be increasingly becoming research hotspot.
Lignite is that a kind of high volatile, high-moisture, high ash content, low heat value, low ash smelting point, chemical reactivity be strong, thermostabilization
Poor, easy-weathering fragmentation, oxidizable spontaneous combustion the inferior fuel of property, is the minimum coal of degree of coalification.Directly lignite is burnt completely unrestrained
Oil, gas and the chemicals in lignite with high added value are taken.The pyrolysis of coal is the important production technology of coal hot-working aspect,
Coal is under conditions of completely cutting off air (or inert atmosphere), the coal tar of low temperature pyrogenation (500~700 DEG C) available high yield
Oil, medium temperature pyrolysis (700~1000 DEG C) can obtain the coal gas of high yield, and high temperature pyrolysis (1000~1200 DEG C) obtains high-quality
The coke of amount.It is domestic largely to carry out lignite upgrading, liquefaction and gas processed using technologies such as lignite pyrolysis and lignite destructive distillation at present, such as
Chinese invention patent application file " low-order coal classified utilization polygenerations systeme and method " (publication number CN105154121A, patent
Application number 201510665313.3), low-order coal is subjected to the quick destructive distillation of low temperature and is handled, raw coke oven gas, tar and semicoke, coal tar are obtained
Oil is further plus hydrogen obtains oil product, and raw coke oven gas obtains coal gas by purified treatment, and semicoke is supplied gas fluidized bed gasification.However utilize lignite
The research and technology for being pyrolyzed adsorbent processed have not been reported.
Chinese invention patent application file " municipal sludge and agricultural wastes oil producing technology for co-pyrolysis " (publication number
CN101643687, application number 200910184253.8) it proposes, to the mixture pyrolysis (400 of municipal sludge and agricultural wastes
~750 DEG C), oil, water-soluble liquid and incoagulability fuel gas can be obtained；Pyrolysis solid product grind can be used as activity
Carbon adsorbent.But the acticarbon hole that this method obtains is undeveloped, specific surface area and Kong Rong little.Usually activity
The preparation of charcoal is needed by carbonizing and activating two stages, and wherein activation process is the most key.Activation mainly divide it is physically activated and
KOH activator activation coal quality or coke raw material are widely used in chemical activation method for chemical activation.But exists with alkali activation and use alkali
Measure big (alkali coke ratio is about 3:1~4:1), complex process, problem at high cost.
In addition, original humic acid is the main feature component that lignite is different from other coals.Alkali density lignite produces humic
Acid is an important directions of lignite comprehensive utilization.Humic acid is widely used to the fields such as metallurgy, chemical industry, agricultural, environmental protection.So
And the utilization of brown coal residue rarely has research after extracting.In humic acid manufacturing works, using conventional caustic extraction method by coal
After middle humic acid dissolution, remaining residue is generally discharged as solid refuse.Also contain one in addition to containing inorganic substances in residue
Quantitative organic matter discharges using the residue as solid refuse, causes the negative influences such as environmental pollution and the wasting of resources.
Chinese invention patent application file " a kind of stepped utilization method of poor quality lignite " (publication number CN104987873A,
Number of patent application 201510269565.4) it proposes, lignite inferior is first subjected to humic acid extraction, then by dry brown coal residue
It is pyrolyzed, production semicoke, tar and raw gas.By humic acid-extraction step, on the one hand obtain that there is relatively wide application
Thus the humic acid of range reduces interior water and coal point in coal simultaneously because the extraction of humic acid, reduces oxygen content in lignite
Existing hydrogen bond between son, facilitates the drying process of lignite.Secondly, the low oxygen content brown coal residue for having extracted humic acid is used for
Pyrolytic process prepares lignite semi-coke, tar and raw gas.Technology disclosed in this document, the pyrolysis temperature to brown coal residue are 400
~750 DEG C, belong to low temperature pyrogenation.The added value for being pyrolyzed obtained solid product semicoke is low, and there is no truly realize lignite
Efficient cascade utilization.
Summary of the invention
The technical problem to be solved in the present invention is that overcoming defect of the existing technology, proposes one kind and taken out by lignite
Propose the method that residue after humic acid prepares adsorbent.Using Lignitic Humic Acid extraction-high temperature pyrolysis as main technological route, to lignite
Staged conversion utilization, i.e. extracted humic acid are carried out, residue is pyrolyzed carbonaceous adsorbent processed, by-product tar and hydrogen-rich gas.Utilize coal
Liquid base after charcoal humic acid extracts in residue, one-step method prepare Cheap highly effective adsorbent, overcome traditional alkali activation legal system
Alkali charge is big (alkali coke ratio is about 3:1~4:1) in standby activated carbon process, complex process, problem at high cost.
The present invention solves technical problem, realizes that the basic ideas of goal of the invention are: extracting coal in conventional alkali-soluble acid analysis method
After middle humic acid, high temperature pyrolysis is carried out to solid residue, high-performance low-cost sorbent, by-product tar and hydrogen-rich gas is made.
The technical solution that the present invention solves the problems, such as, the method that adsorbent is prepared by residue after lignite extracting humic acid, including
Following steps:
Step 1: being dried, being crushed, clean, sieving to lignite, 40 mesh screenings (coal dust) are taken.
Step 2: coal dust is added in the aqueous slkali that mass percent concentration is 2~6%, it is lauched in 50~90 DEG C of temperature
Bath 0.5~3h of heating, the mixture after being reacted.The mass ratio of coal dust and aqueous slkali is 1:20~1:100.
Step 3: filter out supernatant liquor by being centrifugated after the mixture cooling after reaction, obtain humic acid after acid out,
Sediment after centrifugation is the residue extracted after humic acid.
Step 4: the sediment after extracting humic acid is dried at 105~120 DEG C, air or lazy is completely cut off in pyrolysis oven
Property gas shield under, heating pyrolysis, pyrolysis final temperature be 760~940 DEG C, 0.5~4h of constant temperature time.
Step 5: carrying out condensation cooling to pyrolysis gas product, oil water mixture and hydrogen-rich gas can be obtained, grease is mixed
Useful downstream product can be further processed by closing object.
Step 6: the solid matter with deionized water after pyrolysis is washed to neutrality, and drying to constant weight for high temperature, finally obtains
Obtain carbonaceous adsorbent.Temperature is not particularly limited in high temperature described herein, the present invention, and those skilled in the art are according to basic common sense
Set temperature dries the solid product after pyrolysis.The constant weight is also limited without special weighting error index, heat
Solid product after solution, which is dried to, meets adsorbent usage.
The present invention be realize goal of the invention, further improved technical solution is: it is described Step 2: coal dust is pre-oxidized after
It is added to heating water bath in aqueous slkali, the mixture after being reacted.The coal dust method for pre-oxidizing is that quality is added in coal dust
Percent concentration is 5~18%HNO3In solution, solid-liquid mass ratio (coal dust and nitric acid solution mass ratio) is 1:4~1:8,50
0.5~2h of heating water bath at a temperature of~90 DEG C, cooling, filtration washing to neutrality.
In step 2, the aqueous slkali can be NaOH, Na2CO3、Na2P2O7One or more of solution mixture.
The principle of the present invention: humic acid in lignite is extracted using traditional alkali-soluble acid analysis method, alkali is in extracted humic acid process
In destroy Ar-O-C oxygen-containing functional group in coal, on the one hand this effect facilitates the drying process of lignite, on the other hand big
Reduce the generation for being pyrolyzed water in brown coal residue pyrolytic process greatly, reduces the separating difficulty of oil water mixture, improve simultaneously
The quality of tar.Remaining alkali plays the role of semicoke in pyrolytic process to activate reaming in residue, and this effect is main
It is to occur at high temperature, increases substantially burnt absorption property.High temperature is the essential condition for activating pore-creating.At the same time, alkali
With-CH in coal2And-CH- and semicoke react and promote more gas evolutions while activating pore-creating, increase production gas
Amount produces H in gas2It is significantly improved with the content of CO.The present invention can obtain humic acid, carbonaceous by the above staged conversion method
Adsorbent, tar and raw gas product.The method of the present invention is right using Lignitic Humic Acid extraction-high temperature pyrolysis as main technological route
Lignite carries out staged conversion utilization, i.e. extracted humic acid, and residue is pyrolyzed carbonaceous adsorbent processed, by-product tar and hydrogen-rich gas.Benefit
Lye after being extracted with coal humic acid in residue, one-step method high temperature pyrolysis prepare the carbon that specific surface area is high, absorption property is good
Matter adsorbent, overcoming traditional alkali activation method, to prepare in activated carbon process alkali charge big (alkali coke ratio is about 3:1~4:1),
Complex process, problem at high cost.The tar of by-product contains that pyrolysis water is few, and separation is easy in the method for the present invention, and tar yield is high,
The raw gas of by-product has very high H2With CO content, CH4Content is low, is highly suitable as chemical industry original after producing the purified modification of gas
Expect gas.
Detailed description of the invention
Fig. 1 the method for the present invention process flow diagram.
Specific embodiment
Combined with specific embodiments below, the method for the present invention is described in further detail, but the present invention is not by following realities
Apply the limitation of example.
Embodiment 1
Humic acid extracts:
Using air dried Xianfeng Brown as raw material, pulverization process, removal of impurities are carried out using coal pulverizer, screening takes under 40 meshes
Object (coal dust) sealing is collected.Table 1 is the composition analysis of Xianfeng Brown.
1 Xianfeng Brown Industrial Analysis of table, elemental analysis
5 parts of quality 5g coal samples are weighed in three-necked flask, be separately added into 150mL mass percent concentration be 2%, 3%, 4%,
5%, in 6% NaOH solution, heating water bath 3h, 2.5h, 2h, 1h, 0.5h at 90 DEG C, 80 DEG C, 70 DEG C, 60 DEG C, 50 DEG C respectively.
It will be centrifugated after solution cooling after reaction, supernatant liquor taken to boil off moisture, as humate.Under different alkali extracting concentrations
Humate yield it is as shown in table 2.The humate yield highest obtained when it can be seen that being 4% with NaOH concentration.
2 humate yield of table
| Concentration of lye % | 2 | 3 | 4 | 5 | 6 |
| Humate yield % | 13.2 | 14.5 | 18.8 | 18.7 | 15.9 |
In embodiment 1,5 parts of coal samples can be pre-oxidized first, it may be assumed that by coal dust be added mass percent concentration be 5~
18%HNO3In solution, solid-liquid mass ratio (coal dust and nitric acid solution mass ratio) is 1:4~1:8, water-bath at a temperature of 50~90 DEG C
0.5~2h is heated, cooling, filtration washing to neutrality.
Embodiment 2
Pyrolysis:
The air dried Xianfeng Brown 5g of 40~80 mesh is weighed, is lauched for 80 DEG C in the 150mLNaOH solution that concentration is 4%
Bath heating 1h.It will be centrifugated after solution cooling after reaction, sediment is put into 105 in baking ovenoC dries 2h.It is dry to weigh 3g
Brown coal residue is put into pyrolytic reaction pipe, and logical nitrogen does protection gas, and the heating rate of set temperature controller is 10oC/min,
Respectively 760oC and 940oIt is pyrolyzed under C pyrolysis final temperature (being also known as pyrolysis temperature in embodiment), 30 min of constant temperature time.It will pyrolysis
Solid matter with deionized water afterwards is washed to neutrality, and drying to constant weight for high temperature, finally obtains the carbonaceous adsorbent.
It is verified through actual experiment, drying brown coal residue completely cuts off under air or inert gas shielding in pyrolysis oven, heating heat
Solution is pyrolyzed final temperature between 760~940 DEG C, the carbonaceous adsorbent can be obtained between 0.5~4h of constant temperature time, realizes
Goal of the invention.
In order to compare, weighs the dry base Xianfeng Brown 3g of 40~80 mesh and be pyrolyzed in the same way.Table 3 is heat
Solution gained factor of created gase and production gas composition, table 4 are iodine number, specific surface area, Kong Rong and the average pore size of obtained solid product.
Table 3 is pyrolyzed factor of created gase and produces gas composition
As can be seen from the above table, the factor of created gase of brown coal residue is greater than the factor of created gase of raw coal.It is brown to illustrate that the presence of alkali promotes
The orientation conversion of coal residue pyrolysis.The content that brown coal residue pyrolysis produces CO in gas composition is up to 30% or more, (H2+ CO) content
900 oC reaches 78% when being pyrolyzed, (the H being pyrolyzed than lignite under the same terms2+ CO) content it is high by 14.5%.Illustrate brown coal residue
The production gas that high temperature pyrolysis obtains is more suitable for as chemical industry synthesis gas.Higher CO content also illustrates that NaOH had been pyrolyzed simultaneously
Activation has occurred in journey.
The iodine number and pore structure parameter of solid product under the different pyrolysis temperatures of table 4
As can be seen from the above table, the solid product iodine number that Xianfeng Brown is pyrolyzed is lower, what brown coal residue was pyrolyzed
Solid product adsorbance dramatically increases, and this difference is 900oIt is particularly evident when C, illustrate that NaOH is played well at high temperature
Activate reaming effect.In addition, from the N of semicoke2It is burnt hot with Xianfeng Brown that adsorption/desorption isotherms can be seen that brown coal residue pyrolysis
Burnt compare of solution possesses mesoporous more abundant.Brown coal residue 900oC pyrogenically prepared active carbocoal is 612.4 m than table2/ g, hole
Hold up to 0.3928 cm3/ g can be used as adsorbent use.
Embodiment 3
The air dried Xianfeng Brown 5g of 80 mesh or less is weighed, the 300mLNaOH that concentration is 2%, 3%, 4%, 5% is separately added into
In solution, 50oUltrasonic water bath heats 20 min under C.It will be centrifugated after solution cooling after reaction, sediment is put into baking
105 in caseoC dries 2 h.It weighs 3g drying brown coal residue to be put into pyrolytic reaction pipe, logical nitrogen does protection gas, set temperature
The heating rate of controller is 10oC/min, 900oIt is pyrolyzed under C pyrolysis temperature, constant temperature time is 20 min.Table 5 is difference
Alkali concentration extracts iodine number, specific surface area, Kong Rong and the average pore size of brown coal residue pyrolysis coke after humic acid.
Residue pyrolysis burnt iodine number and pore structure parameter after the different alkali concentration extracting Lignitic Humic Acids of table 5
| NaOH concentration/% | Iodine number/(mg/g) | Specific surface area/(m2/g) | Kong Rong/(cm3/g) | Average pore size/nm |
| 3 | 666.7 | 497.5 | 0.2777 | 2.233 |
| 5 | 845.0 | 707.0 | 0.4970 | 2.812 |
Embodiment 4
It is substantially the same manner as Example 3, except that aqueous slkali is Na2CO solution.
Embodiment 5
It is substantially the same manner as Example 3, except that aqueous slkali is NaOH and Na2P2O7Mixture.
Claims (2)
1. a kind of method that residue prepares adsorbent after extracting humic acid by lignite, comprising the following steps:
Step 1: being dried, being crushed, clean, sieving to lignite, coal dust under 40 meshes is taken；
Step 2: heating water bath in aqueous slkali is added to after coal dust is pre-oxidized, the mixture after being reacted；
The coal dust method for pre-oxidizing is that it is 5~18%HNO that mass percent concentration, which is added, in coal dust3In solution, coal dust and nitric acid
Solution quality ratio is 1:4~1:8,0.5~2h of heating water bath at a temperature of 50~90 DEG C, cooling, filtration washing to neutrality；
The mass percent concentration of the aqueous slkali is 2~6%, and the temperature of heating water bath is 50~90 DEG C, heating time is 0.5 ~
The mass ratio of 3h, coal dust and aqueous slkali is 1:20~1:100；
Step 3: filtering out supernatant liquor by being centrifugated after the mixture cooling after reaction, humic acid being obtained after acid out, be centrifuged
Sediment afterwards is the residue extracted after humic acid；
Step 4: completely cutting off after the sediment drying after extracting humic acid under air or inert gas shielding in pyrolysis oven, rising
Warm solution, pyrolysis final temperature are 760~940 DEG C, 0.5~4h of constant temperature time；
Step 5: carrying out condensation cooling to pyrolysis gas product, oil water mixture and hydrogen-rich gas are obtained；
Step 6: the solid matter with deionized water after pyrolysis is washed to neutrality, and drying to constant weight, carbonaceous absorption is obtained
Agent.
2. the method that residue prepares adsorbent after the extracting humic acid according to claim 1 by lignite, it is characterized in that: step
In two, the aqueous slkali is NaOH, Na2CO3、Na2P2O7One or more of solution mixture.
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