CN112717880A - Benzene series adsorbent and preparation method thereof - Google Patents
Benzene series adsorbent and preparation method thereof Download PDFInfo
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- CN112717880A CN112717880A CN201911032960.5A CN201911032960A CN112717880A CN 112717880 A CN112717880 A CN 112717880A CN 201911032960 A CN201911032960 A CN 201911032960A CN 112717880 A CN112717880 A CN 112717880A
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- 125000001997 phenyl group Chemical class [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 title abstract 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 138
- 238000001035 drying Methods 0.000 claims abstract description 60
- 239000013067 intermediate product Substances 0.000 claims abstract description 38
- 230000004048 modification Effects 0.000 claims abstract description 38
- 238000012986 modification Methods 0.000 claims abstract description 38
- 239000002006 petroleum coke Substances 0.000 claims abstract description 23
- 238000011282 treatment Methods 0.000 claims abstract description 22
- 238000010301 surface-oxidation reaction Methods 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 21
- 238000001816 cooling Methods 0.000 claims abstract description 19
- 239000012298 atmosphere Substances 0.000 claims abstract description 11
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 11
- 239000005749 Copper compound Substances 0.000 claims abstract description 7
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 45
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 31
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 30
- 239000000706 filtrate Substances 0.000 claims description 30
- 239000000843 powder Substances 0.000 claims description 30
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 20
- 229910017604 nitric acid Inorganic materials 0.000 claims description 20
- 238000005470 impregnation Methods 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims description 18
- 230000007935 neutral effect Effects 0.000 claims description 17
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 claims description 16
- 239000005750 Copper hydroxide Substances 0.000 claims description 16
- 150000001555 benzenes Chemical class 0.000 claims description 16
- 229910001956 copper hydroxide Inorganic materials 0.000 claims description 16
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 238000000227 grinding Methods 0.000 claims description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229940116318 copper carbonate Drugs 0.000 claims description 5
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 41
- 239000000243 solution Substances 0.000 description 35
- 239000012299 nitrogen atmosphere Substances 0.000 description 27
- 239000000463 material Substances 0.000 description 24
- 238000001914 filtration Methods 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 239000010949 copper Substances 0.000 description 10
- 239000012855 volatile organic compound Substances 0.000 description 10
- 238000005516 engineering process Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- JBGWMRAMUROVND-UHFFFAOYSA-N 1-sulfanylidenethiophene Chemical compound S=S1C=CC=C1 JBGWMRAMUROVND-UHFFFAOYSA-N 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 6
- 230000003213 activating effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000008096 xylene Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000002912 waste gas Substances 0.000 description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 238000001994 activation Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000006065 biodegradation reaction Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 238000007385 chemical modification Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005265 energy consumption 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
- 125000000524 functional group Chemical group 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Natural products C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- -1 methane hydrocarbon Chemical class 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 230000000241 respiratory effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 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
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by adsorption, e.g. preparative gas chromatography
-
- 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
- B01J20/3078—Thermal treatment, e.g. calcining or pyrolizing
-
- 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
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/70—Organic compounds not provided for in groups B01D2257/00 - B01D2257/602
- B01D2257/708—Volatile organic compounds V.O.C.'s
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Carbon And Carbon Compounds (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a benzene series adsorbent and a preparation method thereof, petroleum coke is dried, and strong base and a divalent copper compound are added and fully mixed; carrying out high-temperature treatment on the mixture under the inert atmosphere condition; cooling the sample, washing and drying to obtain an active carbon intermediate product; carrying out surface oxidation modification on the active carbon intermediate product; drying and low-temperature treatment under inert atmosphere. The modified activated carbon prepared by the invention is used for benzene series adsorption, and has higher adsorption selectivity and adsorption capacity.
Description
Technical Field
The invention belongs to the field of waste gas treatment, and particularly relates to a benzene series adsorbent and a preparation method thereof.
Background
Volatile Organic Compounds (VOCs) have become an important source of atmospheric pollution, and the control and remediation of VOCs has become one of the key points in environmental protection. Along with the distribution of the emission standards of pollutants for the petroleum refining industry (GB 31570-2015) and the emission standards of pollutants for the petrochemical industry (GB 31571-2015), and the distribution of the emission charge trial solution for volatile organic pollutants, the requirement of waste gas treatment in the petrochemical industry is more and more strict. Therefore, the research and development of economic and efficient prevention and treatment technologies and the elimination of the atmospheric environmental pollution of VOCs are urgent.
At present, VOCs treatment technologies mainly comprise absorption, adsorption, condensation, combustion, photocatalytic oxidation, biodegradation, low-temperature plasma treatment technologies and the like. Compared with other treatment technologies, the adsorption method has the advantages of good purification effect, low energy consumption and low operating cost, and is an ideal VOCs treatment technology. Common adsorbents include activated carbon, biomass materials, silica, and the like. Activated carbon adsorption is a typical adsorption method, but the VOCs are adsorbed by using the activated carbon only, so that physical adsorption is mainly used, the adsorption capacity is small, and the adsorption effect needs to be improved. The activated carbon is subjected to chemical modification and other treatments, so that chemical adsorption is generated in the process of adsorbing organic substances, the adsorption performance of the adsorbent can be effectively improved, and the adsorption capacity is increased.
Some technologies for treating organic waste gas by activated carbon adsorption have been developed, but none of the technologies can break through the dynamic adsorption and desorption laws of organic matters on the surface of activated carbon, which are disclosed in empirical formulas of frandrichs and langmuir adsorption, i.e. the gas phase partial pressure of pollutants is lower than a certain value and then can not be adsorbed on the activated carbon adsorbent, so that the activated carbon adsorption is used for treating high-concentration organic waste gas, and the requirement that the total non-methane hydrocarbon content is lower than 120mg/m specified in GB31571-2015 is met3The emission limit of (2) requires the configuration of a multi-stage activated carbon adsorption tower, and the investment and operation cost will increase exponentially. In addition, the difference of adsorption capacities of different components in the same waste gas is large in the active carbon adsorption, and the research and development of adsorbents are needed according to different pollutants.
CN103623774A discloses a preparation method of modified activated carbon for fuel oil desulfurization, which is to add distilled water into a reactor, add sodium hydroxide solution to adjust the pH value to 6.8-14.3, then add activated carbon, and introduce mixed gas of ozone and air while stirring to carry out surface oxidation reaction on the activated carbon; and after the reaction is finished, taking out the activated carbon, washing the activated carbon with distilled water, drying the washed activated carbon, and cooling the dried activated carbon to room temperature to prepare the modified activated carbon for adsorbing the organic thiophene sulfide in the fuel oil. The invention utilizes ozone to modify the active carbon in liquid phase, can obviously increase the acidic oxygen-containing groups on the surface of the active carbon, and improves the adsorption capacity of the organic thiophene sulfide. However, the modified activated carbon is developed for adsorbing organic thiophene sulfide in fuel oil, and has poor adsorption selectivity for benzene series.
CN103041788A discloses an adsorbent for removing thiophene sulfides in gasoline, wherein the adsorbent is a spherical activated carbon material loaded with copper elements; the content of the copper element is 0.5-5% of the total weight of the adsorbent, and the copper element is in a simple substance state. The preparation method comprises the following steps: (a) ion exchanging the granular raw material with a soluble copper salt solution; (b) drying the copper-loaded particulate feedstock of step (a); (c) calcining the dried particles of step (b); (d) activating the calcined particles of step (c) with an activating agent. The adsorbent uses weak acidic phenolic cation exchange resin as a precursor, copper is loaded on the precursor through ion exchange, and then carbonization and CO are carried out2And in the activation process, the adsorbent with good sphericity and high mechanical strength is obtained. The adsorbent has higher adsorption capacity and adsorption selectivity to thiophene sulfides, and the preparation raw materials are easy to obtain, and the preparation method is simple. However, the adsorbent has good adsorption effect and adsorption selectivity for thiophene sulfides in the exhaust gas, and the adsorption effect on benzene series substances is not good.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a benzene series adsorbent and a preparation method thereof. The method takes petroleum coke as a raw material, synthesizes the activated carbon material through in-situ modification, and then carries out surface modification, the preparation method is simple, and the prepared modified activated carbon is used for benzene series adsorption and has higher adsorption selectivity and adsorption capacity.
The invention provides a preparation method of a benzene series adsorbent, which comprises the following steps: (1) drying petroleum coke, adding strong base and a divalent copper compound, and fully mixing; (2) carrying out high-temperature treatment on the mixture under the inert atmosphere condition; (3) cooling the sample, washing and drying to obtain an active carbon intermediate product; (4) carrying out surface oxidation modification on the active carbon intermediate product; (5) and drying the modified sample, and treating at low temperature under an inert atmosphere.
In the invention, the strong base in the step (1) is potassium hydroxide and the like. The mass ratio of the strong base to the petroleum coke is 0.1: 1-10: 1, and preferably 1: 1-6: 1.
In the present invention, the divalent copper compound in the step (1) is at least one of copper hydroxide, basic copper carbonate, and the like, and is preferably copper hydroxide. The mass ratio of the petroleum coke to the divalent copper compound is 50: 1-3: 1, preferably 30: 1-5: 1.
In the invention, the inert atmosphere in the step (2) is one of nitrogen, helium, argon and the like. The temperature of the high-temperature treatment is 600-1000 ℃, preferably 700-900 ℃, and the treatment time is 0.05-3 h, preferably 0.16-1 h. Further, the high-temperature treatment is carried out in the presence of microwaves, wherein the frequency of the microwaves is 2450MHz, and the power is 0.5-1.0 kw.
In the invention, the cooling in the step (3) is carried out under the protection of nitrogen. Grinding the sample obtained in the step (3) into powder before washing, adopting an acid solution with the pH value not more than 7, wherein the acid solution is one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid and the like, and the concentration is 5-25 wt%, uniformly mixing, and then carrying out solid-liquid separation until the pH value of the filtrate is neutral.
In the invention, the drying in the step (3) is carried out under the vacuum condition, and the vacuum degree is-500-0 kPa.
In the invention, the modifier used for the surface oxidation modification in the step (4) is at least one of nitric acid solution, hydrogen peroxide solution and the like, preferably nitric acid solution, and the concentration of the nitric acid solution is 0.01-16 mol/L, preferably 0.2-10 mol/L. The mass ratio of the modifier to the intermediate product of the activated carbon is 200: 1-0.1: 1, preferably 20: 1-1: 1. Specifically, one of an isometric impregnation method, a supersaturation impregnation method and the like can be adopted, the supersaturation impregnation method is preferred, and the modification time is 0.5-72 hours, preferably 6-24 hours.
In the invention, the drying temperature in the steps (1), (3) and (5) is 60-150 ℃, preferably 80-120 ℃, and the drying time is 2-10 hours, preferably 4-8 hours.
In the invention, the inert atmosphere in the step (5) is one of nitrogen, helium, argon and the like. The low-temperature treatment temperature is 300-600 ℃, preferably 400-500 ℃, and the treatment time is 0.5-24 hours, preferably 3-12 hours.
The benzene series adsorbent is prepared by the method. The specific surface area of the prepared adsorbent is 1700-3600 m2A pore volume of 0.85-1.35 cm/g3The iodine adsorption value is 1500-3950 mg/g, and the Cu loading is 1.5-7.8 wt.%.
Compared with the prior art, the method has the following advantages:
(1) the invention introduces Cu in the petroleum coke activation treatment process2+In-situ synthesizing Cu-containing high-specific-surface-area activated carbon; then, surface oxidation is carried out on the surface of the material, and functional groups such as hydroxyl, carboxyl, phenolic hydroxyl and the like are introduced; under the conditions of proper temperature and inert atmosphere, Cu2+Under the action of hydroxyl, carboxyl and phenolic hydroxyl functional groups, spontaneous reduction reaction is carried out to generate the Cu with a valence state+，Cu+The empty S orbit is easier to form sigma bonds with pi electrons of benzene series in the VOCs, and pi complexation occurs, so that the selectivity of the empty S orbit on the benzene series in the VOCs is improved.
(2) The adsorbent prepared by the invention has higher adsorption selectivity and adsorption capacity for benzene series in VOCs.
Detailed Description
The method and effects of the present invention will be described in detail with reference to examples. The embodiments are implemented on the premise of the technical scheme of the invention, and detailed implementation modes and specific operation processes are given, but the protection scope of the invention is not limited by the following embodiments. In the present invention, wt.% is a mass fraction.
The experimental procedures in the following examples are, unless otherwise specified, conventional in the art. The experimental materials used in the following examples were purchased from a conventional biochemical reagent store unless otherwise specified.
In the following examples and comparative examples, low temperature N was used for the specific surface area and pore size distribution of the samples2The content of the benzene series is measured by an adsorption method, the content of the benzene series is measured by a GC-FID/DB-WAX capillary column, and the copper load is detected by an ICP instrument.
Example 1
Taking 100g of petroleum coke, drying for 5h at 100 ℃, uniformly mixing with 300g of potassium hydroxide and 10g of copper hydroxide, and treating for 0.4h at 900 ℃ in a nitrogen atmosphere. The sample is cooled under the protection of nitrogen, ground into powder and added into a hydrochloric acid solution with the concentration of 10 weight percent for washing until the pH value of the filtrate is neutral. Then drying for 6h at 150 ℃ to obtain an active carbon intermediate product. Taking 40g of the activated carbon intermediate product, carrying out surface oxidation modification by using 100g of nitric acid solution with the concentration of 4mol/L, adopting supersaturated impregnation modification for 24h, filtering out solids, and drying at 120 ℃ for 4 h. The dried activated carbon was treated at 400 ℃ for 12h under nitrogen atmosphere and the resulting material was designated AC-1.
Example 2
Taking 100g of petroleum coke, drying for 5h at 100 ℃, uniformly mixing with 200g of potassium hydroxide and 4g of copper hydroxide, and treating for 0.3h at 700 ℃ in a nitrogen atmosphere. The sample is cooled under the protection of nitrogen, ground into powder and added into a 10wt% sulfuric acid solution for washing until the pH value of the filtrate is neutral. Then drying for 6h at 150 ℃ to obtain an active carbon intermediate product. Taking 40g of the activated carbon intermediate product, carrying out surface oxidation modification by using 100g of nitric acid solution with the concentration of 8mol/L, adopting supersaturated impregnation modification for 24h, filtering out solids, and drying at 120 ℃ for 4 h. The dried activated carbon was treated at 400 ℃ for 12h under nitrogen atmosphere and the resulting material was designated AC-2.
Example 3
Taking 100g of petroleum coke, drying for 5h at 100 ℃, uniformly mixing with 400g of potassium hydroxide and 20g of copper hydroxide, and treating for 1h at 1000 ℃ in a nitrogen atmosphere. Cooling the sample under the protection of nitrogen, grinding the sample into powder, adding the powder into 20wt% acetic acid solution for washing until the pH value of the filtrate is neutral, and then drying the filtrate at 150 ℃ for 6 hours to obtain an activated carbon intermediate product. Taking 40g of the activated carbon intermediate product, carrying out surface oxidation modification by using 400g of nitric acid solution with the concentration of 15mol/L, adopting supersaturated impregnation modification for 24h, filtering out solids, and drying at 120 ℃ for 4 h. The dried activated carbon was treated at 450 ℃ for 12h under nitrogen atmosphere and the resulting material was designated AC-3.
Example 4
Taking 100g of petroleum coke, drying for 5h at 100 ℃, uniformly mixing with 300g of potassium hydroxide and 20g of basic copper carbonate, and treating for 0.4h at 900 ℃ in a nitrogen atmosphere. And cooling the sample under the protection of nitrogen, grinding the sample into powder, adding the powder into a hydrochloric acid solution with the concentration of 10wt% for washing until the pH value of the filtrate is neutral, and then drying the filtrate at 150 ℃ for 6 hours to obtain an activated carbon intermediate product. Taking 40g of the activated carbon intermediate product, carrying out surface oxidation modification by using 100g of nitric acid solution with the concentration of 4mol/L, adopting supersaturated impregnation modification for 24h, filtering out solids, and drying at 120 ℃ for 4 h. And (3) treating the dried activated carbon at 400 ℃ for 12h under the condition of a nitrogen atmosphere, and marking the obtained material as AC-4.
Example 5
Drying 100g petroleum coke at 100 deg.C for 5 hr, mixing with 300g potassium hydroxide and 13g copper carbonate, and treating at 900 deg.C for 0.4 hr under nitrogen atmosphere.
And cooling the sample under the protection of nitrogen, grinding the sample into powder, adding the powder into a hydrochloric acid solution with the concentration of 10wt% for washing until the pH value of the filtrate is neutral, and then drying the filtrate at 150 ℃ for 6 hours to obtain an activated carbon intermediate product. Taking 40g of the activated carbon intermediate product, carrying out surface oxidation modification by using 100g of nitric acid solution with the concentration of 4mol/L, adopting supersaturated impregnation modification for 24h, filtering out solids, and drying at 120 ℃ for 4 h. And (3) treating the dried activated carbon at 400 ℃ for 12h under the condition of a nitrogen atmosphere, and marking the obtained material as AC-5.
Example 6
Taking 100g of petroleum coke, drying for 5h at 100 ℃, uniformly mixing with 300g of potassium hydroxide and 10g of copper hydroxide, and treating for 0.4h at 900 ℃ in a helium atmosphere. And cooling the sample under the protection of nitrogen, grinding the sample into powder, adding the powder into a hydrochloric acid solution with the concentration of 10wt% for washing until the pH value of the filtrate is neutral, and then drying the filtrate at 150 ℃ for 6 hours to obtain an activated carbon intermediate product. Taking 40g of the activated carbon intermediate product, carrying out surface oxidation modification by using 100g of nitric acid solution with the concentration of 4mol/L, adopting supersaturated impregnation modification for 24h, filtering out solids, and drying at 120 ℃ for 4 h. And (3) treating the dried activated carbon at 400 ℃ for 12h under the helium atmosphere, and marking the obtained material as AC-6.
Example 7
Drying 100g petroleum coke at 100 deg.C for 5 hr, mixing with 300g potassium hydroxide and 10g copper hydroxide, placing in microwave reactor with microwave frequency of 2450MHz and power of 1kw, and activating at 900 deg.C for 0.4 hr under nitrogen atmosphere. Cooling the sample, grinding the sample into powder, adding the powder into a hydrochloric acid solution with the concentration of 10wt% for washing until the pH value of the filtrate is neutral, and then drying the filtrate at 150 ℃ for 6 hours to obtain an activated carbon intermediate product. Taking 40g of the activated carbon intermediate product, carrying out surface oxidation modification by using 100g of nitric acid solution with the concentration of 4mol/L, adopting supersaturated impregnation modification for 24h, filtering out solids, and drying at 120 ℃ for 4 h. And treating the dried activated carbon at 400 ℃ for 12h under the condition of a nitrogen atmosphere, and marking the obtained material as AC-7.
Example 8
Taking 100g of petroleum coke, drying for 5h at 100 ℃, uniformly mixing with 300g of potassium hydroxide and 10g of copper hydroxide, and treating for 0.4h at 900 ℃ in a nitrogen atmosphere. And cooling the sample under the protection of nitrogen, grinding the sample into powder, adding the powder into a hydrochloric acid solution with the concentration of 10wt% for washing until the pH value of the filtrate is neutral, and then drying the filtrate at 150 ℃ for 6 hours to obtain an activated carbon intermediate product. Taking 40g of activated carbon intermediate product, carrying out surface oxidation modification by using 100g of hydrogen peroxide solution with the concentration of 4mol/L, adopting supersaturated impregnation modification for 24h, filtering out solid, and drying at 120 ℃ for 4 h. And treating the dried activated carbon at 400 ℃ for 12h under the condition of a nitrogen atmosphere, and marking the obtained material as AC-8.
Example 9
Taking 100g of petroleum coke, drying for 5h at 100 ℃, uniformly mixing with 300g of potassium hydroxide and 10g of copper hydroxide, and treating for 0.4h at 900 ℃ in a nitrogen atmosphere. And cooling the sample under the protection of nitrogen, grinding the sample into powder, adding the powder into a hydrochloric acid solution with the concentration of 10wt% for washing until the pH value of the filtrate is neutral, and then drying the filtrate for 6 hours at the temperature of 100 ℃ under the condition of-300 kPa to obtain an activated carbon intermediate product. Taking 40g of an activated carbon intermediate product, carrying out surface oxidation modification by using 100g of nitric acid solution with the concentration of 4mol/L, adopting supersaturated impregnation modification for 24h, filtering out a solid, and drying at 120 ℃ for 4 h. And treating the dried activated carbon at 400 ℃ for 12h under the condition of a nitrogen atmosphere, and marking the obtained material as AC-9.
Comparative example 1
Drying 100g of coconut shell carbonized material at 100 ℃ for 5h, uniformly mixing with 300g of potassium hydroxide and 10g of copper hydroxide, and treating at 900 ℃ for 0.4h in a nitrogen atmosphere. And cooling the sample under the protection of nitrogen, grinding the sample into powder, adding the powder into a hydrochloric acid solution with the concentration of 10wt% for washing until the pH value of the filtrate is neutral, and then drying the filtrate at 150 ℃ for 6 hours to obtain an activated carbon intermediate product. Taking 40g of the activated carbon intermediate product, carrying out surface oxidation modification by using 100g of nitric acid solution with the concentration of 4mol/L, adopting supersaturated impregnation modification for 24h, filtering out solids, and drying at 120 ℃ for 4 h. And treating the dried activated carbon at 400 ℃ for 12h under the condition of a nitrogen atmosphere to obtain the material D-1.
Comparative example 2
Taking 100g of petroleum coke, drying for 5h at 100 ℃, uniformly mixing with 300g of potassium carbonate and 10g of copper hydroxide, and treating for 0.4h at 900 ℃ in a nitrogen atmosphere. And cooling the sample under the protection of nitrogen, grinding the sample into powder, adding the powder into a hydrochloric acid solution with the concentration of 10wt% for washing until the pH value of the filtrate is neutral, and then drying the filtrate at 150 ℃ for 6 hours to obtain an activated carbon intermediate product. Taking 40g of the activated carbon intermediate product, carrying out surface oxidation modification by using 100g of nitric acid solution with the concentration of 4mol/L, adopting supersaturated impregnation modification for 24h, filtering out solids, and drying at 120 ℃ for 4 h. And (3) treating the dried activated carbon for 12 hours at the temperature of 400 ℃ under the nitrogen atmosphere, and recording the obtained material as D-2.
Comparative example 3
Taking 100g of petroleum coke, drying for 5h at 100 ℃, uniformly mixing with 300g of potassium hydroxide and 10g of nickel hydroxide, and activating for 0.4h at 900 ℃ in a nitrogen atmosphere. And cooling the sample under the protection of nitrogen, grinding the sample into powder, adding the powder into a hydrochloric acid solution with the concentration of 10wt% for washing until the pH value of the filtrate is neutral, and then drying the filtrate at 150 ℃ for 6 hours to obtain an activated carbon intermediate product. Taking 40g of the activated carbon intermediate product, carrying out surface oxidation modification by using 100g of nitric acid solution with the concentration of 4mol/L, adopting supersaturated impregnation modification for 24h, filtering out solids, and drying at 120 ℃ for 4 h. And (3) treating the dried activated carbon for 12 hours at the temperature of 400 ℃ under the nitrogen atmosphere, and recording the obtained material as D-3.
Comparative example 4
Taking 100g of petroleum coke, drying for 5h at 100 ℃, uniformly mixing with 300g of potassium hydroxide and 10g of copper hydroxide, and activating for 0.4h at 900 ℃ in a nitrogen atmosphere. And cooling the sample under the protection of nitrogen, grinding the sample into powder, adding the powder into a hydrochloric acid solution with the concentration of 10wt% for washing until the pH value of the filtrate is neutral, and then drying the filtrate at 150 ℃ for 6 hours to obtain an activated carbon intermediate product. 40g of the activated carbon intermediate product was taken and treated at 400 ℃ for 12h under a nitrogen atmosphere, and the obtained material was designated as D-4.
Comparative example 5
Taking 100g of petroleum coke, drying for 5h at 100 ℃, uniformly mixing with 300g of potassium hydroxide and 10g of copper hydroxide, and treating for 0.4h at 900 ℃ in a nitrogen atmosphere. And cooling the sample under the protection of nitrogen, grinding the sample into powder, adding the powder into a hydrochloric acid solution with the concentration of 10wt% for washing until the pH value of the filtrate is neutral, and then drying the filtrate at 150 ℃ for 6 hours to obtain an activated carbon intermediate product. Taking 40g of an activated carbon intermediate product, carrying out surface oxidation modification by using 100g of nitric acid solution with the concentration of 4mol/L, adopting supersaturated impregnation modification for 24h, filtering out a solid, and drying at 120 ℃ for 4h to obtain the material D-5.
Comparative example 6
Taking 100g of petroleum coke, drying for 5h at 100 ℃, uniformly mixing with 300g of sodium hydroxide and 10g of copper hydroxide, and treating for 0.4h at 900 ℃ in a nitrogen atmosphere. And cooling the sample under the protection of nitrogen, grinding the sample into powder, adding the powder into a hydrochloric acid solution with the concentration of 10wt% for washing until the pH value of the filtrate is neutral, and then drying the filtrate at 150 ℃ for 6 hours to obtain an activated carbon intermediate product. Taking 40g of the activated carbon intermediate product, carrying out surface oxidation modification by using 100g of nitric acid solution with the concentration of 4mol/L, adopting supersaturated impregnation modification for 24h, filtering out solids, and drying at 120 ℃ for 4 h. And (3) treating the dried activated carbon for 12 hours at the temperature of 400 ℃ under the condition of a nitrogen atmosphere, and marking the obtained material as D-6.
Comparative example 7
The procedure used in CN103623774A example 1 was followed to give the material D-7.
Comparative example 8
The difference from example 1 is that: the preparation method of CN103041788A example 1 is adopted, and the material is marked as D-8.
Test example 1
The adsorbing materials prepared in examples 1 to 9 of the present invention and comparative examples 1 to 8 were used for the adsorption of benzene series. Respiratory gas generated in benzene storage tank area of a certain refinery, benzene concentration is 2.7 multiplied by 104 mg/m3Adsorbing at normal temperature and normal pressure, and setting the benzene content at the outlet of the adsorption tank to be lower than 4mg/m3When the benzene content is higher than 4mg/m3The adsorption results are shown in Table 1, where the time is the point of penetration of the adsorbent.
TABLE 1 Properties of benzene-series adsorbents
Test example 2
The adsorbing materials prepared in the invention example 1 and the comparative examples 1 to 7 are respectively used for adsorbing toluene and xylene gas, wherein the concentration of the toluene is 1133mg/m3The xylene concentration is 285.3mg/m3Adsorbing at normal temperature and normal pressure, setting the toluene or xylene content at the outlet of the adsorption tank to be lower than 4mg/m3When the toluene or xylene content is higher than 4mg/m3And at the point of sorbent breakthrough. The adsorption results are shown in table 2.
TABLE 2 Properties of benzene-series adsorbents
As can be seen from tables 1 and 2, the adsorbent prepared by the invention has good adsorption selectivity and adsorption capacity for benzene series.
Claims (16)
1. A preparation method of a benzene series adsorbent is characterized by comprising the following steps: (1) drying petroleum coke, adding strong base and a divalent copper compound, and fully mixing; (2) carrying out high-temperature treatment on the mixture under the inert atmosphere condition; (3) cooling the sample, washing and drying to obtain an active carbon intermediate product; (4) carrying out surface oxidation modification on the active carbon intermediate product; (5) and drying the modified sample, and treating at low temperature under an inert atmosphere.
2. The method of claim 1, wherein: the strong base in the step (1) is potassium hydroxide, and the mass ratio of the strong base to the petroleum coke is 0.1: 1-10: 1, preferably 1: 1-6: 1.
3. The method of claim 1, wherein: the divalent copper compound in the step (1) is at least one of copper hydroxide, basic copper carbonate and copper carbonate, and is preferably copper hydroxide.
4. A method according to claim 1 or 3, characterized in that: the mass ratio of the petroleum coke to the divalent copper compound in the step (1) is 50: 1-3: 1, preferably 30: 1-5: 1.
5. The method of claim 1, wherein: the high-temperature treatment temperature in the step (2) is 600-1000 ℃, preferably 700-900 ℃, and the treatment time is 0.05-3 hours, preferably 0.16-1 hour.
6. The method according to claim 1 or 5, characterized in that: the high-temperature treatment in the step (2) is carried out in the presence of microwave, the frequency of the microwave is 2450MHz, and the power is 0.5-1.0 kw.
7. The method of claim 1, wherein: and (4) cooling under the protection of nitrogen.
8. The method according to claim 1 or 7, characterized in that: and (3) grinding the cooled sample into powder, and washing with an acid solution with the pH value not more than 7 until the pH value of the filtrate is neutral.
9. The method of claim 8, wherein: the acid solution is one or more of hydrochloric acid, sulfuric acid, nitric acid, acetic acid and the like, and the concentration is 5-25 wt%.
10. The method of claim 1, wherein: and (4) drying under a vacuum condition, wherein the vacuum degree is-500-0 kPa.
11. The method of claim 1, wherein: modifying agent adopted in the surface oxidation modification in the step (4) is at least one of nitric acid solution and hydrogen peroxide solution, preferably nitric acid solution; the concentration of the modifier is 0.01-16 mol/L, preferably 0.2-10 mol/L.
12. The method according to claim 1 or 11, characterized in that: the mass ratio of the modifier to the activated carbon intermediate product in the step (4) is 200: 1-0.1: 1, preferably 20: 1-1: 1.
13. The method according to claim 1 or 12, characterized in that: the modification adopts one of an isometric impregnation method and a supersaturation impregnation method, and the modification time is 0.5-72 h.
14. The method of claim 1, wherein: the drying temperature of the steps (1), (3) and (5) is 60-150 ℃, preferably 80-120 ℃, and the drying time is 2-10 hours, preferably 4-8 hours.
15. The method of claim 1, wherein: the low-temperature treatment temperature in the step (5) is 300-600 ℃, preferably 400-500 ℃, and the treatment time is 0.5-24 hours, preferably 3-12 hours.
16. A benzene-based adsorbent, characterized in that it is prepared by the process according to any one of claims 1 to 15.
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