CN110075793A - A kind of nano-carbon material and its preparation method and use of damaged tire preparation - Google Patents
A kind of nano-carbon material and its preparation method and use of damaged tire preparation Download PDFInfo
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- CN110075793A CN110075793A CN201910302281.9A CN201910302281A CN110075793A CN 110075793 A CN110075793 A CN 110075793A CN 201910302281 A CN201910302281 A CN 201910302281A CN 110075793 A CN110075793 A CN 110075793A
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- Prior art keywords
- carbon material
- nano
- damaged tire
- preparation
- drying
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
The invention belongs to technical field of desulfurization, are related to the nano-carbon material and its preparation method and use of a kind of damaged tire preparation, the application specially in gasoline absorbing desulfurization.In preparation process include the pre-treatment of damaged tire, then add sodium bicarbonate to pre-process with fermentation method in obtained sample, finally carries out calcination processing and obtain the nano-carbon material of ultra-fine grain.Present invention process is simple, and sodium bicarbonate and carbon material are carried out mixed calcining in the synthesis process, and obtained carbon material is to the adsorption activity with higher of sulfide in fuel oil, and the dosage of adsorbent is few, and production cost is low, and obtained oil quality is high.Adsorbent recycling convenience, it is recyclable to be used for multiple times.
Description
Technical field
The invention belongs to technical field of desulfurization, refer in particular to a kind of nano-carbon material as made from damaged tire and its synthetic method with
And its application in gasoline desulfurization.
Background technique
With the increase of vapour vehicle fleet size, the burning of sulfurous fuels will cause serious air pollution, therefore control fuel oil
Middle sulfur content can effectively reduce pollution from source.The sulfur content in diesel oil is reduced, realizes that low-sulfur diesel oil is the following oil refining
Attention of the inexorable trend of industry development with countries in the world to environmental problem, common removing mercaptan technology industrial at present have
S-zorb technology, alkali process method etc., but S-zorb technology can generate by-product in adsorption process, influence the circulation of adsorbent
The disadvantages of use；And alkali process method is easy to cause to corrode to equipment, therefore using damaged tire as raw material, passes through the fermentation method of green
Pretreatment calcine again, prepare mercaptan of the nano-carbon material under room temperature, condition of normal pressure in adsorbing and removing gasoline can overcome it is above
Deficiency.And this method preparation carbon material structural property (partial size is small) and surface chemistry (functional group) be to absorption property with
Selectivity has important influence.
Summary of the invention
The invention reside in provide the nano-carbon material of ultra-fine grain.The present invention also provides above-mentioned receiving by damaged tire preparation
The preparation method of rice carbon material.Another purport of the invention is the provision of the application of above-mentioned adsorbent, and has excellent
Absorption property.
To realize above-mentioned experiment purpose, preparation method includes washing damaged tire with KOH solution, then filtering drying, is added
NaHCO3Mixed grinding calcining is finally washed to neutral nano-carbon material obtained by drying.
A kind of synthetic method of the nano-carbon material of damaged tire preparation, includes the following steps:
(1) a certain amount of damaged tire is mixed with appropriate KOH, distilled water stirring is added, obtains black mixture, filtration washing
Afterwards, it is put into air dry oven drying；
(2) black solid for taking out drying, weighs a certain amount of drying damaged tire and NaHCO3Ground and mixed is uniform；
(3) mixed-powder obtained by step 2) is poured into corundum crucible, is put into tube furnace and leads to nitrogen calcining；
(4) calcined powder is taken out, washing is filtered to it, until washing neutrality, baking oven is finally putting into, after drying
Up to nano-carbon material
In step (1), the usage ratio of the damaged tire, KOH and distilled water be 5~7g:9.5~10.5g:45~
55mL, the damaged tire are particle of the size in 1~3mm.
In step (1), the drying temperature is 75~85 DEG C, and drying time is 11~13h.
In step (2), the damaged tire and NaHCO3Mass ratio be 0.75~1.25:1.25~1.75.
In step (3), the calcination temperature is 750~850 DEG C, and heating rate is 5~8 DEG C/min, calcination time 1
~2h.
In step (4), the oven temperature is 75~85 DEG C, and drying time is 11~13h.
The nano-carbon material of the ultra-fine grain as made from damaged tire of above method preparation, specific surface area are 78~100m2/
0.29~0.33cm of g, Kong Rongwei3/ g, partial size are 59~76.9nm.
Ultra-fine grain nano-carbon material prepared by the present invention is used for the purposes of adsorbing and removing sulfur in gasoline alcohols sulfide,
Such as the adsorption reaction of amyl hydrosulfide, the adsorbent show higher adsorption activity, excellent performance to removing mercaptan from gasoline
It is mainly due to following factors.
1) contain basic functionality in carbon material, and mercaptan has acidity, therefore the adsorbent has good adsorptivity
Energy.
2) sodium bicarbonate is added and calcines three times of the increase of carbon material specific surface area obtained, and big specific surface area is conducive to inhale
It is attached.
The ultra-fine grain nano-carbon material as made from damaged tire to thio-alcohol sulfide removal efficiency with higher in oil product,
The ultra-deep removing of amyl hydrosulfide that can be 30ppm by initial sulfur content in 3h.
The invention has the benefit that
1) nano-carbon material prepared by the present invention is mixed using different amounts of sodium bicarbonate with carbon material in synthesis step
Calcining changes the structure of carbon material；Have many advantages, such as that grain diameter is small, adsorption activity is high, can overcome it is in the prior art not
Foot such as consumes the corrosion of big and equipment；
2) can be promoted carbon material to the simple recycling of the adsorbing and removing ability of mercaptan from gasoline and adsorbent and
It is recycled, finally realizes the target of sulfur-containing compound in ultra-deep removing fuel oil.And carbon material is in adsorbing and removing gasoline
During mercaptan, without using organic solvent.
Detailed description of the invention
Fig. 1 is carbon material and NaHCO3Mixed proportion is not simultaneously to the absorption property comparison diagram of amyl hydrosulfide.
Specific embodiment
With reference to the accompanying drawing and specific embodiment further illustrates the contents of the present invention.
Embodiment 1
A kind of preparation method of the nano-carbon material as made from damaged tire, including the following steps:
1) 6g damaged tire and 10.2g KOH are weighed in beaker, 50mL distilled water is added, stirs 12h at 60 DEG C.
2) it washs, black solid is filtered by vacuum to obtain, dry 12h at 80 DEG C takes black solid 1g and 1g NaHCO after dry3
Mixture is put into heating tube furnace and is warming up to 800 DEG C with the rate of 5 DEG C/min, keep 1h, then drops naturally by ground and mixed
Temperature.
3) black product in tube furnace is taken out, is washed to neutrality, 80 DEG C of baking oven drying 12h is then placed into, obtains
The nano-carbon material as made from damaged tire of ultra-fine grain, is denoted as C-1.
Synthesized nano-carbon material, specific surface area 78m2/ g, average grain diameter 76.9nm.
Embodiment 2
A kind of preparation method of the nano-carbon material as made from damaged tire, including the following steps:
1) 6g damaged tire and 10.2g KOH are weighed in beaker, 50ml distilled water is added, stirs 12h at 60 DEG C.
2) it washs, black solid is filtered by vacuum to obtain, dry 12h at 80 DEG C takes black solid 1g and 1.5g after dry
NaHCO3Mixture is put into heating tube furnace and is warming up to 800 DEG C with the rate of 5 DEG C/min, keeps 1h, then by ground and mixed
Temperature fall.
3) black product in tube furnace is taken out, is washed to neutrality, 80 DEG C of baking oven drying 12h is then placed into, obtains
The nano-carbon material as made from damaged tire of ultra-fine grain, is denoted as C-2.
Synthesized nano-carbon material, specific surface area 99m2/ g, average grain diameter 60.4nm.
Embodiment 3
A kind of preparation method of the nano-carbon material as made from damaged tire, including the following steps:
1) 6g damaged tire and 10.2g KOH are weighed in beaker, 50mL distilled water is added, stirs 13h at 60 DEG C.
2) it washs, black solid is filtered by vacuum to obtain, dry 12h at 85 DEG C takes black solid 1g and 2g NaHCO after dry3
Mixture is put into heating tube furnace and is warming up to 800 DEG C with the rate of 5 DEG C/min, keep 1h, then drops naturally by ground and mixed
Temperature.
3) black product in tube furnace is taken out, is washed to neutrality, 80 DEG C of baking oven drying 12h is then placed into, obtains
The nano-carbon material as made from damaged tire of ultra-fine grain, is denoted as C-3.
Synthesized nano-carbon material, specific surface area 83m2/ g, average grain diameter 72.6nm.
Comparative example 1
A kind of preparation method of the nano-carbon material as made from damaged tire, including the following steps:
1) 6g damaged tire and 10.2g KOH are weighed in beaker, 50ml distilled water is added, stirs 12h at 60 DEG C.
2) it washs, black solid is filtered by vacuum to obtain, black solid is put into heating tubular type after drying by dry 12h at 80 DEG C
800 DEG C are warming up to the rate of 5 DEG C/min in furnace, 1h is kept, obtains the carbon material as made from damaged tire, be denoted as C.
Embodiment 4
A kind of preparation method of the nano-carbon material as made from damaged tire, including the following steps:
1) 5g damaged tire and 9.5g KOH are weighed in beaker, 45mL distilled water is added, stirs 12h at 60 DEG C.
2) it washs, black solid is filtered by vacuum to obtain, dry 11h at 80 DEG C takes black solid 0.75g and 1.25g after dry
NaHCO3Mixture is put into heating tube furnace and is warming up to 750 DEG C with the rate of 5 DEG C/min, keeps 1h, then by ground and mixed
Temperature fall.
3) black product in tube furnace is taken out, is washed to neutrality, 75 DEG C of baking oven drying 11h is then placed into, obtains
The nano-carbon material as made from damaged tire of ultra-fine grain.
Embodiment 5
A kind of preparation method of the nano-carbon material as made from damaged tire, including the following steps:
1) 7g damaged tire and 10.5gKOH are weighed in beaker, 55mL distilled water is added, stirs 13h at 60 DEG C.
2) it washs, black solid is filtered by vacuum to obtain, dry 13h at 85 DEG C takes black solid 1.25g and 1.75g after dry
NaHCO3Mixture is put into heating tube furnace and is warming up to 850 DEG C with the rate of 8 DEG C/min, keeps 2h, then by ground and mixed
Temperature fall.
3) black product in tube furnace is taken out, is washed to neutrality, 85 DEG C of baking oven drying 13h is then placed into, obtains
The nano-carbon material as made from damaged tire of ultra-fine grain.
Desulfurization
The resulting ultra-fine grain nano-carbon material of embodiment 2 is used to adsorb the sulfur-containing compound in abjection oil product, specifically
Process is as follows, and 0.05g nano-carbon material is added in 50mL conical flask, and 20mL sulfur content is the simulation oil of 30ppm.Carry out constant temperature
Water-bath oscillating reactions.After reaction, oil sample is drawn with the syringe with filter membrane, then carries out the analysis of sulfur content by GC.
The absorption property such as Fig. 1 of nano-carbon material to amyl hydrosulfide, the results showed that mix 1g carbon material with 1.5g NaHCO3
The nano-carbon material being prepared is calcined in the experiment of adsorbing and removing mercaptan, the reaction time to pass through 180min, adsorbs desulfurization degree
It is 99.7%, is able to achieve the deep removal of mercaptan, meets the requirement of state six.
Claims (8)
1. a kind of synthetic method of the nano-carbon material of damaged tire preparation, which comprises the steps of:
(1) a certain amount of damaged tire is mixed with appropriate KOH, distilled water stirring is added, obtains black mixture, after filtration washing,
It is put into air dry oven drying；
(2) black solid for taking out drying, weighs a certain amount of drying damaged tire and NaHCO3Ground and mixed is uniform；
(3) mixed-powder obtained by step 2) is poured into corundum crucible, is put into tube furnace and leads to nitrogen calcining；
(4) it takes out calcined powder, washing is filtered to it, until washing neutrality, be finally putting into baking oven, after drying to obtain the final product
Nano-carbon material.
2. a kind of synthetic method of the nano-carbon material of damaged tire preparation as described in claim 1, which is characterized in that step
(1) in, the usage ratio of the damaged tire, KOH and distilled water is 5~7g:9.5~10.5g:45~55mL, and described is useless
Tire is particle of the size in 1~3mm.
3. a kind of synthetic method of the nano-carbon material of damaged tire preparation as described in claim 1, which is characterized in that step
(1) in, the drying temperature is 75~85 DEG C, and drying time is 11~13h.
4. a kind of synthetic method of the nano-carbon material of damaged tire preparation as described in claim 1, which is characterized in that step
(2) in, the damaged tire and NaHCO3Mass ratio be 0.75~1.25:1.25~1.75.
5. a kind of synthetic method of the nano-carbon material of damaged tire preparation as described in claim 1, which is characterized in that step
(3) in, the calcination temperature is 750~850 DEG C, and heating rate is 5~8 DEG C/min, and calcination time is 1~2h.
6. a kind of synthetic method of the nano-carbon material of damaged tire preparation as described in claim 1, which is characterized in that step
(4) in, the oven temperature is 75~85 DEG C, and drying time is 11~13h.
7. a kind of nano-carbon material of damaged tire preparation, which is characterized in that be by the synthesis of any one of claim 1~6
What method was prepared, specific surface area is 78~100m20.29~0.33cm of/g, Kong Rongwei3/ g, partial size are 59~76.9nm.
8. a kind of nano-carbon material of damaged tire preparation as claimed in claim 7 is used for the vulcanization of adsorbing and removing sulfur in gasoline alcohols
The purposes in object space face.
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|---|---|---|---|---|
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2019
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| CN102512933A (en) * | 2011-12-05 | 2012-06-27 | 詹钦 | Method for treating and utilizing oxidation sweetening tail gas |
| CN107236329A (en) * | 2016-03-29 | 2017-10-10 | 河南沐桐环保产业有限公司 | A kind of method that junked tire prepares carbon black |
| CN108203588A (en) * | 2018-01-30 | 2018-06-26 | 中国石油大学(华东) | A kind of method of nitrogen atmosphere low temperature pyrogenation processing damaged tire |
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