CN110605106A - A regeneration method of waste mercury catalyst activated carbon after detoxification treatment - Google Patents
A regeneration method of waste mercury catalyst activated carbon after detoxification treatment Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 239000002699 waste material Substances 0.000 title claims abstract description 52
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 48
- 238000011069 regeneration method Methods 0.000 title claims abstract description 43
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000001784 detoxification Methods 0.000 title abstract description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 99
- 230000008929 regeneration Effects 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 18
- 230000010355 oscillation Effects 0.000 claims abstract description 12
- 230000001172 regenerating effect Effects 0.000 claims abstract description 7
- 238000001914 filtration Methods 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 30
- 238000010438 heat treatment Methods 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- -1 polypropylene Polymers 0.000 claims description 14
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 8
- 239000001110 calcium chloride Substances 0.000 claims description 8
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 229920001155 polypropylene Polymers 0.000 claims description 7
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 7
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 7
- 239000000047 product Substances 0.000 claims description 7
- 238000005260 corrosion Methods 0.000 claims description 6
- 230000007797 corrosion Effects 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 4
- 239000000706 filtrate Substances 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 238000002955 isolation Methods 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000004064 recycling Methods 0.000 claims 1
- 239000000126 substance Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 6
- 238000011084 recovery Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract 1
- 238000001179 sorption measurement Methods 0.000 description 37
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 13
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 13
- 229910052740 iodine Inorganic materials 0.000 description 13
- 239000011630 iodine Substances 0.000 description 13
- 229960000907 methylthioninium chloride Drugs 0.000 description 13
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 7
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000007789 gas Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000000292 calcium oxide Substances 0.000 description 5
- 235000012255 calcium oxide Nutrition 0.000 description 5
- 239000012299 nitrogen atmosphere Substances 0.000 description 5
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 239000004800 polyvinyl chloride Substances 0.000 description 3
- 238000012216 screening Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000005997 Calcium carbide Substances 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 239000002920 hazardous waste Substances 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 229940101209 mercuric oxide Drugs 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3416—Regenerating or reactivating of sorbents or filter aids comprising free carbon, e.g. activated carbon
-
- 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
- B01J20/34—Regenerating or reactivating
- B01J20/345—Regenerating or reactivating using a particular desorbing compound or mixture
- B01J20/3475—Regenerating or reactivating using a particular desorbing compound or mixture in the liquid phase
-
- 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
- B01J20/34—Regenerating or reactivating
- B01J20/3483—Regenerating or reactivating by thermal treatment not covered by groups B01J20/3441 - B01J20/3475, e.g. by heating or cooling
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
本发明公开了一种无害化处理后的废汞触媒活性炭的再生方法，属于废汞触媒的回收再利用技术领域。本发明将无害化处理后的废汞触媒中的活性炭先置于盐酸溶液中振荡，盐酸溶液浓度为0.2~0.8 mol/L，振荡时间为0.5~4 h；过滤后置于隔氧环境中升温至650~850℃，维持0.5~4 h，冷却得到再生活性炭。本发明提供的化学再生与热再生相结合的处理工艺所需设备简单，再生时间短，再生效果好，采用较低成本即可实现废汞触媒中活性炭的再生利用，具有明显的经济效益与环保意义。The invention discloses a method for regenerating activated carbon of waste mercury catalysts after harmless treatment, and belongs to the technical field of recovery and reuse of waste mercury catalysts. In the present invention, the activated carbon in the waste mercury catalyst after detoxification treatment is first placed in the hydrochloric acid solution for oscillation, the concentration of the hydrochloric acid solution is 0.2-0.8 mol/L, and the oscillation time is 0.5-4 h; after filtering, it is placed in an oxygen-isolated environment Raise the temperature to 650-850°C, maintain it for 0.5-4 h, and cool to obtain regenerated activated carbon. The treatment process of the combination of chemical regeneration and thermal regeneration provided by the invention requires simple equipment, short regeneration time and good regeneration effect, and the regeneration and utilization of activated carbon in the waste mercury catalyst can be realized at a relatively low cost, which has obvious economic benefits and environmental protection significance.
Description
技术领域technical field
本发明属于废汞触媒的回收再利用技术领域，具体涉及一种无害化处理后的废汞触媒活性炭的再生方法。The invention belongs to the technical field of recovery and reuse of waste mercury catalysts, and in particular relates to a method for regenerating activated carbon of waste mercury catalysts after harmless treatment.
背景技术Background technique
汞触媒是电石法生产聚氯乙烯（PVC）不可或缺的部分，其用作PVC生产中乙炔和氯化氢气体合成氯乙烯（VCM）的催化剂。汞触媒的生产是以活性炭作载体、氯化汞为活性物质，将氯化汞负载于活性炭表面。汞触媒在使用一定时间后，其活性下降需进行更换，更换下来的废汞触媒，一般依然含有2％～5％左右的氯化汞。而氯化汞剧毒，极易挥发，且易溶于水，若将更换下来的汞触媒直接进行丢弃或堆放，势必将造成严重的汞污染，产生重大安全隐患。根据《废汞触媒处理处置方法（GB/T 36382-2008）》，目前针对废汞触媒的无害化处理主要采用蒸馏法与控氧干馏法。其中蒸馏法的原理为加入生石灰、氢氧化钠等将废汞触媒中各价态的汞转化为极易分解、挥发、收集的物理化学性质相近的同类物质（绝大部分为氧化汞），氧化汞受热分解为单质汞与氧气，并对单质汞蒸气进行淬冷，实现废汞触媒中汞的回收。Mercury catalyst is an indispensable part of the production of polyvinyl chloride (PVC) by the calcium carbide method, and it is used as a catalyst for the synthesis of vinyl chloride (VCM) from acetylene and hydrogen chloride gas in the production of PVC. The production of mercury catalyst is based on activated carbon as carrier, mercury chloride as active substance, and mercury chloride is loaded on the surface of activated carbon. After the mercury catalyst has been used for a certain period of time, its activity decreases and needs to be replaced. The replaced waste mercury catalyst generally still contains about 2% to 5% of mercury chloride. Mercury chloride is highly toxic, highly volatile, and easily soluble in water. If the replaced mercury catalyst is discarded or stacked, it will inevitably cause serious mercury pollution and cause major safety hazards. According to the "Waste Mercury Catalyst Treatment and Disposal Methods (GB/T 36382-2008)", the current harmless treatment of waste mercury catalysts mainly adopts distillation and oxygen-controlled dry distillation. The principle of the distillation method is to add quicklime, sodium hydroxide, etc. to convert the mercury in various valence states in the waste mercury catalyst into similar substances with similar physical and chemical properties that are easily decomposed, volatilized, and collected (mostly mercuric oxide). Mercury is decomposed into elemental mercury and oxygen by heat, and the elemental mercury vapor is quenched to realize the recovery of mercury in the waste mercury catalyst.
虽然通过该方法实现了废汞触媒的无害化处理与汞的回收，但没有实现活性炭的活化再生，且由于在预处理工序中引入了生石灰、氢氧化钠等物质，使得废汞触媒在经过之后的蒸馏工序后表面附着了大量碳酸钙、氧化钙、碳酸钠等粉末，这使得活性炭严重失活，进而造成活性炭难以被再度利用。虽然废汞触媒经过回收汞的无害化处理后，原则上可以作为一般废物进行处理，但人们总是会担心某一批次活性炭的汞含量是否会超过危险废物的鉴别标准。不仅如此，活性炭无法回收利用造成了严重的资源浪费，提高了企业生产成本。Although the harmless treatment of the waste mercury catalyst and the recovery of mercury have been realized by this method, the activation and regeneration of activated carbon has not been realized, and due to the introduction of quicklime, sodium hydroxide and other substances in the pretreatment process, the waste mercury catalyst has passed through After the subsequent distillation process, a large amount of calcium carbonate, calcium oxide, sodium carbonate and other powders adhered to the surface, which seriously deactivated the activated carbon, making it difficult to reuse the activated carbon. Although the waste mercury catalyst can be disposed of as general waste in principle after the harmless treatment of mercury recovery, people always worry about whether the mercury content of a certain batch of activated carbon will exceed the identification standard of hazardous waste. Not only that, the inability to recycle activated carbon has caused a serious waste of resources and increased the production cost of enterprises.
发明内容Contents of the invention
为了实现废汞触媒无害化处理后废活性炭的高值利用，本发明的目的是提供一种低成本、流程简单、效果好的废汞触媒活性炭再生方法。本发明利用盐酸化学再生与热再生相结合的方法，使其表面和内部存在的碳酸钙、碳酸钠、氧化钙、残留PVC等物质脱除，恢复活性炭吸附能力，从而实现再生的目的。In order to realize the high-value utilization of waste activated carbon after waste mercury catalyst harmless treatment, the purpose of the present invention is to provide a low-cost, simple process and good effect regeneration method for waste mercury catalyst activated carbon. The present invention uses hydrochloric acid chemical regeneration and thermal regeneration to remove calcium carbonate, sodium carbonate, calcium oxide, residual PVC and other substances existing on the surface and inside, restore the adsorption capacity of activated carbon, and achieve the purpose of regeneration.
本发明的目的通过以下技术方案实现：一种无害化处理后的废汞触媒活性炭的再生方法，包括如下步骤：The object of the present invention is achieved through the following technical solutions: a method for regeneration of waste mercury catalyst activated carbon after harmless treatment, comprising the steps of:
(1) 将无害化处理后的废汞触媒活性炭置于浓度为0.2~0.8 mol/L的盐酸溶液中，采用振荡器振荡，振荡时间为0.5~4 h；(1) Place the detoxified waste mercury catalyst activated carbon in a hydrochloric acid solution with a concentration of 0.2-0.8 mol/L, and vibrate with an oscillator for 0.5-4 h;
(2) 将步骤(1)得到的混合溶液进行过滤分离得到滤液和活性炭，滤液返回步骤(1)中重复利用；(2) The mixed solution obtained in step (1) is filtered and separated to obtain filtrate and activated carbon, and the filtrate is returned to step (1) for reuse;
(3) 将过滤后的活性炭产物置入程序升温加热炉中，在隔氧条件下升温至650~850℃，保持温度活化再生0.5~4 h；(3) Put the filtered activated carbon product into a temperature-programmed heating furnace, raise the temperature to 650-850 °C under the condition of oxygen isolation, and keep the temperature for activation and regeneration for 0.5-4 h;
(4) 关闭加热炉冷却，得到再生活性炭。(4) Close the heating furnace to cool down to obtain regenerated activated carbon.
本发明中，步骤(1)中，活性炭与盐酸投放质量比为1:5~1:10。In the present invention, in step (1), the mass ratio of activated carbon to hydrochloric acid is 1:5 to 1:10.
本发明中，步骤(1)中，盐酸浓度为0.4~0.8 mol/L，振荡时间为0.5 h。In the present invention, in step (1), the concentration of hydrochloric acid is 0.4-0.8 mol/L, and the shaking time is 0.5 h.
本发明中，步骤(1)中，振荡器采用翻转式振荡器，频率为20~50 rpm。In the present invention, in step (1), the oscillator adopts a flip-type oscillator with a frequency of 20-50 rpm.
本发明中，步骤(2)中，首先采用聚丙烯或聚四氟乙烯耐腐材质滤板进行活性炭与盐酸溶液分离，然后向废盐酸溶液中加入稀硫酸去除反应产生的氯化钙，再次分离，最后将滤出的盐酸溶液返回步骤(1)实现重复使用。Among the present invention, in step (2), at first adopt polypropylene or polytetrafluoroethylene anticorrosion material filter plate to carry out activated carbon and hydrochloric acid solution separation, then add dilute sulfuric acid to the calcium chloride that removal reaction produces in waste hydrochloric acid solution, separate again , and finally the hydrochloric acid solution filtered out is returned to step (1) to realize reuse.
本发明中，步骤(3)中，温度为700~750 ℃，再生时间为2~2.5 h；在密闭隔氧环境加热，以避免活性炭烧失。In the present invention, in step (3), the temperature is 700-750°C, and the regeneration time is 2-2.5 h; heating is carried out in a closed oxygen-isolated environment to avoid burning of the activated carbon.
和现有技术相比，本发明具有以下优点：Compared with the prior art, the present invention has the following advantages:
1、本发明采用化学再生与热再生相结合的方式实现了对无害化处理后废汞触媒活性炭的再生，相对于单一的活性炭再生方法，具有效果好，成本低，设备简单等特点；1. The present invention realizes the regeneration of waste mercury catalyst activated carbon after harmless treatment by combining chemical regeneration and thermal regeneration. Compared with a single activated carbon regeneration method, it has the characteristics of good effect, low cost, and simple equipment;
2、本发明在化学再生过程中采用盐酸在振荡器振荡作用下，短时间内即可快速清除废汞触媒活性炭表面残留的碳酸钙、碳酸钠、氧化钙等物质，提高活性炭的吸附能力；2. In the chemical regeneration process, the present invention uses hydrochloric acid under the vibration of the oscillator to quickly remove calcium carbonate, sodium carbonate, calcium oxide and other substances remaining on the surface of the waste mercury catalyst activated carbon in a short period of time, so as to improve the adsorption capacity of the activated carbon;
3、本发明采用热再生方式对无害化处理后废汞触媒活性炭进行再生，快速清除了活性炭内部残留的吸附物质，显著恢复了无害化处理后废汞触媒活性炭的吸附能力。3. The present invention adopts the thermal regeneration method to regenerate the waste mercury catalyst activated carbon after detoxification treatment, quickly removes the residual adsorption substances inside the activated carbon, and significantly restores the adsorption capacity of the waste mercury catalyst activated carbon after detoxification treatment.
具体实施方式Detailed ways
以下将结合具体实施例，进一步阐述本发明。这些实施例仅用于说明本发明并非对保护范围的限制。The present invention will be further described below in conjunction with specific examples. These examples are only used to illustrate the present invention and not to limit the scope of protection.
工艺筛选试验：Process Screening Test:
1.盐酸浓度与振荡时间的筛选1. Screening of hydrochloric acid concentration and shaking time
(1)将无害化处理后的废汞触媒活性炭平均分为20份，置于不同浓度（0.2 mol/L，0.4mol/L，0.6 mol/L，0.8 mol/L）盐酸溶液中，振荡一定时间（0.5 h，1 h，1.5 h，2 h）后关闭设备，过滤干燥得到不同盐酸浓度与振荡时间条件处理后的再生活性炭。(1) Divide the detoxified waste mercury catalyst activated carbon into 20 parts on average, place them in hydrochloric acid solutions with different concentrations (0.2 mol/L, 0.4 mol/L, 0.6 mol/L, 0.8 mol/L), shake After a certain period of time (0.5 h, 1 h, 1.5 h, 2 h), the equipment was turned off, filtered and dried to obtain regenerated activated carbon treated with different concentrations of hydrochloric acid and shaking time.
(2)检测步骤(1)中不同处理条件得到的再生活性炭的碘吸附值与亚甲基蓝吸附值，结果表明，再生时间一定，当盐酸浓度值由0.2 mol/L升高至0.4 mol/L时，碘吸附值与亚甲基蓝吸附值均有较大上升，但超过0.6 mol/L后无明显增加；当盐酸浓度值在0.4~0.8mol/L范围内，振荡时间对再生活性炭吸附性能影响不大，0.5 h的振荡时间已经足够。因此本发明优选盐酸浓度为0.4~0.8 mol/L，振荡时间为0.5 h，最佳条件盐酸浓度值为0.6mol/L，振荡时间为0.5 h。(2) The iodine adsorption value and the methylene blue adsorption value of the regenerated activated carbon obtained by different treatment conditions in the detection step (1), the results show that the regeneration time is constant, when the concentration of hydrochloric acid increases from 0.2 mol/L to 0.4 mol/L, Both iodine adsorption value and methylene blue adsorption value increased significantly, but there was no significant increase after exceeding 0.6 mol/L; when the concentration of hydrochloric acid was in the range of 0.4-0.8 mol/L, the oscillation time had little effect on the adsorption performance of regenerated activated carbon, and 0.5 The oscillation time of h is sufficient. Therefore, the preferred concentration of hydrochloric acid in the present invention is 0.4-0.8 mol/L, and the oscillation time is 0.5 h. The optimal condition is that the concentration of hydrochloric acid is 0.6 mol/L, and the oscillation time is 0.5 h.
2.热再生温度与时间的筛选2. Screening of thermal regeneration temperature and time
(1)将盐酸浓度值为0.6 mol/L，振荡时间为0.5 h条件下处理后的活性炭平均分为12份，置入程序升温炉，设置温度分别为650 ℃，750 ℃，850 ℃，在隔绝氧气环境下进行处理，保持时间为0.5 h，1 h，1.5 h，2 h，处理结束后关闭设备，冷却，得到不同热再生温度与时间条件处理后的再生活性炭。(1) The activated carbon treated under the condition of hydrochloric acid concentration of 0.6 mol/L and shaking time of 0.5 h was divided into 12 parts on average, and placed in a temperature-programmed furnace with the set temperatures of 650 °C, 750 °C, and 850 °C, respectively. The treatment was carried out in an oxygen-isolated environment, and the holding time was 0.5 h, 1 h, 1.5 h, and 2 h. After the treatment, the equipment was closed and cooled to obtain regenerated activated carbon treated under different thermal regeneration temperatures and time conditions.
(2)检测步骤(1)中不同处理条件得到的再生活性炭的碘吸附值与亚甲基蓝吸附值，结果表明，热再生时间一定时，再生活性炭的吸附性能随着温度升高先增加后降低，温度为750 ℃时效果最佳；在热处理温度一定时，活性炭随着保持时间的增加而上升，但超过2 h后增加幅度较低，考虑到时间成本与能耗，选取保持时间为2 h时最佳。因此本发明选取热再生温度为650~850 ℃，再生时间为0.5~4 h；优选的，热再生温度为700~750 ℃，再生时间为2~2.5 h；最佳条件热再生温度为750 ℃，维持时间为2 h。(2) The iodine adsorption value and the methylene blue adsorption value of the regenerated activated carbon obtained by different treatment conditions in the detection step (1), the results show that when the thermal regeneration time is constant, the adsorption performance of the regenerated activated carbon increases first and then decreases with the increase of temperature, and the temperature The effect is best when the heat treatment temperature is 750 ℃; when the heat treatment temperature is constant, the activated carbon increases with the increase of the holding time, but the increase rate is low after more than 2 h. Considering the time cost and energy consumption, the best holding time is selected as 2 h. good. Therefore, the present invention selects the thermal regeneration temperature as 650-850 °C, and the regeneration time as 0.5-4 h; preferably, the thermal regeneration temperature is 700-750 °C, and the regeneration time is 2-2.5 h; the optimum thermal regeneration temperature is 750 °C , and the maintenance time is 2 h.
实施例1Example 1
一种涉及无害化处理后的废汞触媒活性炭的再生方法，具体步骤如下：A method for regenerating waste mercury catalyst activated carbon after harmless treatment, the specific steps are as follows:
(1)将20 g无害化处理后的废汞触媒活性炭投入到0.7 mol/L的盐酸溶液中，活性炭与盐酸投放质量比为1:5，使用翻转式振荡器，振荡频率为30 rpm，振荡2 h取下；(1) Put 20 g of waste mercury catalyst activated carbon after detoxification treatment into 0.7 mol/L hydrochloric acid solution, the mass ratio of activated carbon to hydrochloric acid is 1:5, use a flipping oscillator, and the oscillation frequency is 30 rpm, Shake for 2 h and remove;
(2)采用聚丙烯或聚四氟乙烯等耐腐材质滤板将步骤(1)的活性炭与盐酸溶液分离，向废盐酸溶液中加入适量稀硫酸去除反应产生的氯化钙，再次分离，并将滤出的盐酸溶液返回步骤(1)实现重复使用；(2) Adopt corrosion-resistant material filter plates such as polypropylene or polytetrafluoroethylene to separate the gac of step (1) from the hydrochloric acid solution, add an appropriate amount of dilute sulfuric acid to remove the calcium chloride produced by the reaction in the waste hydrochloric acid solution, separate again, and The hydrochloric acid solution filtered out is returned to step (1) to realize reuse;
(3)将过滤后的活性炭产物置入程序升温加热炉中，在氮气气氛，气体流量为0.5 L/min，650 ℃条件下加热3 h，以保证密闭隔氧环境；(3) Put the filtered activated carbon product into a temperature-programmed heating furnace, and heat it at 650 °C for 3 h in a nitrogen atmosphere with a gas flow rate of 0.5 L/min to ensure a closed and oxygen-isolated environment;
(4)关闭加热炉冷却，得到再生活性炭。(4) Close the heating furnace for cooling to obtain regenerated activated carbon.
本实施例根据GB/T 7702.7-2008与GB/T 7702.6-2008测定碘吸附值与亚甲基蓝吸附值，活性炭再生前后的碘吸附值分别为10 mg/g和943 mg/g，亚甲基蓝吸附值分别为1.5 mg/g和152 mg/g，经再生的无害化处理后废汞触媒活性炭恢复了较高吸附能力。This embodiment measures iodine adsorption value and methylene blue adsorption value according to GB/T 7702.7-2008 and GB/T 7702.6-2008. The iodine adsorption value before and after activated carbon regeneration is 10 mg/g and 943 mg/g respectively, and the methylene blue adsorption value is respectively 1.5 mg/g and 152 mg/g, the waste mercury catalyst activated carbon recovered a higher adsorption capacity after regeneration and harmless treatment.
实施例2Example 2
(1)将20 g无害化处理后的废汞触媒活性炭投入到0.6 mol/L的盐酸溶液中，活性炭与盐酸投放质量比为1:6，使用翻转式振荡器，振荡频率为30 rpm，振荡0.5 h取下；(1) Put 20 g of waste mercury catalyst activated carbon after harmless treatment into 0.6 mol/L hydrochloric acid solution, the mass ratio of activated carbon to hydrochloric acid is 1:6, use a flipping oscillator, and the oscillation frequency is 30 rpm, Shake for 0.5 h and take it off;
(2)采用聚丙烯或聚四氟乙烯等耐腐材质滤板将步骤(1)的活性炭与盐酸溶液分离，向废盐酸溶液中加入适量稀硫酸去除反应产生的氯化钙，再次分离，并将滤出的盐酸溶液返回步骤(1)实现重复使用；(2) Adopt corrosion-resistant material filter plates such as polypropylene or polytetrafluoroethylene to separate the gac of step (1) from the hydrochloric acid solution, add an appropriate amount of dilute sulfuric acid to remove the calcium chloride produced by the reaction in the waste hydrochloric acid solution, separate again, and The hydrochloric acid solution filtered out is returned to step (1) to realize reuse;
(3)将过滤后的活性炭产物置入程序升温加热炉中，在氮气气氛，气体流量为0.5 L/min，750 ℃条件下加热2 h，以保证密闭隔氧环境；(3) Put the filtered activated carbon product into a temperature-programmed heating furnace, and heat it at 750 °C for 2 h in a nitrogen atmosphere with a gas flow rate of 0.5 L/min to ensure an airtight oxygen barrier environment;
(4)关闭加热炉冷却，得到再生活性炭。(4) Close the heating furnace for cooling to obtain regenerated activated carbon.
本实施例根据GB/T 7702.7-2008与GB/T 7702.6-2008测定碘吸附值与亚甲基蓝吸附值，活性炭再生前后的碘吸附值分别为10 mg/g和1005 mg/g，亚甲基蓝吸附值分别为1.5 mg/g和159 mg/g，经再生的无害化处理后废汞触媒活性炭恢复了较高吸附能力。This embodiment measures iodine adsorption value and methylene blue adsorption value according to GB/T 7702.7-2008 and GB/T 7702.6-2008. The iodine adsorption value before and after activated carbon regeneration is 10 mg/g and 1005 mg/g respectively, and the methylene blue adsorption value is respectively 1.5 mg/g and 159 mg/g, the waste mercury catalyst activated carbon recovered a higher adsorption capacity after regeneration and harmless treatment.
实施例3Example 3
(1) 将20 g无害化处理后的废汞触媒活性炭投入到0.5 mol/L的盐酸溶液中，活性炭与盐酸投放质量比为1:7，使用翻转式振荡器，振荡频率为30 rpm，振荡0.5 h取下；(1) Put 20 g of waste mercury catalyst activated carbon after detoxification treatment into 0.5 mol/L hydrochloric acid solution, the mass ratio of activated carbon to hydrochloric acid is 1:7, use an overturning oscillator, and the oscillation frequency is 30 rpm, Shake for 0.5 h and take it off;
(2)用聚丙烯或聚四氟乙烯等耐腐材质滤板将步骤(1)的活性炭与盐酸溶液分离，向废盐酸溶液中加入适量稀硫酸去除反应产生的氯化钙，再次分离，并将滤出的盐酸溶液返回步骤(1)实现重复使用；(2) separate the active carbon of step (1) from the hydrochloric acid solution with a corrosion-resistant material filter plate such as polypropylene or polytetrafluoroethylene, add an appropriate amount of dilute sulfuric acid to remove the calcium chloride produced by the reaction in the waste hydrochloric acid solution, separate again, and The hydrochloric acid solution filtered out is returned to step (1) to realize reuse;
(3) 将过滤后的活性炭产物置入程序升温加热炉中，在氮气气氛，气体流量为0.5 L/min，850 ℃条件下加热2 h，以保证密闭隔氧环境；(3) Put the filtered activated carbon product into a temperature-programmed heating furnace, and heat it at 850 °C for 2 h in a nitrogen atmosphere with a gas flow rate of 0.5 L/min to ensure a closed oxygen-barrier environment;
(4)关闭加热炉冷却，得到再生活性炭。(4) Close the heating furnace for cooling to obtain regenerated activated carbon.
本实施例根据GB/T 7702.7-2008与GB/T 7702.6-2008测定碘吸附值与亚甲基蓝吸附值，活性炭再生前后的碘吸附值分别为10 mg/g和965 mg/g，亚甲基蓝吸附值分别为1.5 mg/g和149 mg/g，经再生的无害化处理后废汞触媒活性炭恢复了较高吸附能力。This example measures iodine adsorption value and methylene blue adsorption value according to GB/T 7702.7-2008 and GB/T 7702.6-2008. The iodine adsorption value before and after activated carbon regeneration is 10 mg/g and 965 mg/g respectively, and the methylene blue adsorption value is respectively 1.5 mg/g and 149 mg/g, the waste mercury catalyst activated carbon recovered a higher adsorption capacity after regeneration and harmless treatment.
实施例4Example 4
(1) 将50 g无害化处理后的废汞触媒活性炭投入到0.8 mol/L的盐酸溶液中，活性炭与盐酸投放质量比为1:10，使用翻转式振荡器，振荡频率为30 rpm，振荡4 h取下；(1) Put 50 g of waste mercury catalyst activated carbon after harmless treatment into 0.8 mol/L hydrochloric acid solution, the mass ratio of activated carbon to hydrochloric acid is 1:10, use a flipping oscillator, and the oscillation frequency is 30 rpm, Shake for 4 h and remove;
(2) 采用聚丙烯或聚四氟乙烯等耐腐材质滤板将步骤(1)的活性炭与盐酸溶液分离，向废盐酸溶液中加入适量稀硫酸去除反应产生的氯化钙，再次分离，并将滤出的盐酸溶液返回步骤(1)实现重复使用；(2) adopt corrosion-resistant material filter plates such as polypropylene or polytetrafluoroethylene to separate the gac of step (1) from the hydrochloric acid solution, add an appropriate amount of dilute sulfuric acid to the waste hydrochloric acid solution to remove the calcium chloride produced by the reaction, separate again, and The hydrochloric acid solution filtered out is returned to step (1) to realize reuse;
(3) 将过滤后的活性炭产物置入程序升温加热炉中，在氮气气氛，气体流量为0.5 L/min，850 ℃条件下加热0.5 h，以保证密闭隔氧环境；(3) Put the filtered activated carbon product into a temperature-programmed heating furnace, and heat it for 0.5 h at 850 °C in a nitrogen atmosphere with a gas flow rate of 0.5 L/min to ensure a closed oxygen-barrier environment;
(4) 关闭加热炉冷却，得到再生活性炭。(4) Close the heating furnace to cool down to obtain regenerated activated carbon.
本实施例根据GB/T 7702.7-2008与GB/T 7702.6-2008测定碘吸附值与亚甲基蓝吸附值，活性炭再生前后的碘吸附值分别为10 mg/g和987 mg/g，亚甲基蓝吸附值分别为1.5 mg/g和151 mg/g，经再生的无害化处理后废汞触媒活性炭恢复了较高吸附能力。This example measures iodine adsorption value and methylene blue adsorption value according to GB/T 7702.7-2008 and GB/T 7702.6-2008. The iodine adsorption value before and after activated carbon regeneration is 10 mg/g and 987 mg/g respectively, and the methylene blue adsorption value is respectively 1.5 mg/g and 151 mg/g, the waste mercury catalyst activated carbon recovered a higher adsorption capacity after regeneration and harmless treatment.
实施例5Example 5
(1)将1 kg无害化处理后的废汞触媒活性炭投入到0.4 mol/L的盐酸溶液中，活性炭与盐酸投放质量比为1:9，使用翻转式振荡器，振荡频率为30 rpm，振荡3 h取下；(1) Put 1 kg of waste mercury catalyst activated carbon after detoxification treatment into 0.4 mol/L hydrochloric acid solution, the mass ratio of activated carbon to hydrochloric acid is 1:9, use an overturning oscillator, and the oscillation frequency is 30 rpm, Shake for 3 h and remove;
(2)采用聚丙烯或聚四氟乙烯等耐腐材质滤板将步骤(1)的活性炭与盐酸溶液分离，向废盐酸溶液中加入适量稀硫酸去除反应产生的氯化钙，再次分离，并将滤出的盐酸溶液返回步骤(1)实现重复使用；(2) Adopt corrosion-resistant material filter plates such as polypropylene or polytetrafluoroethylene to separate the gac of step (1) from the hydrochloric acid solution, add an appropriate amount of dilute sulfuric acid to remove the calcium chloride produced by the reaction in the waste hydrochloric acid solution, separate again, and The hydrochloric acid solution filtered out is returned to step (1) to realize reuse;
(3)将过滤后的活性炭产物置入程序升温加热炉中，在氮气气氛，气体流量为5 L/min，750 ℃条件下加热4 h，以保证密闭隔氧环境；(3) Put the filtered activated carbon product into a temperature-programmed heating furnace, and heat it at 750 °C for 4 h in a nitrogen atmosphere with a gas flow rate of 5 L/min to ensure a closed and oxygen-insulated environment;
(4) 关闭加热炉冷却，得到再生活性炭。(4) Close the heating furnace to cool down to obtain regenerated activated carbon.
本实施例根据GB/T 7702.7-2008与GB/T 7702.6-2008测定碘吸附值与亚甲基蓝吸附值，活性炭再生前后的碘吸附值分别为10 mg/g和998 mg/g，亚甲基蓝吸附值分别为1.5 mg/g和153 mg/g，经再生的无害化处理后废汞触媒活性炭恢复了较高吸附能力。In this example, according to GB/T 7702.7-2008 and GB/T 7702.6-2008, the iodine adsorption value and methylene blue adsorption value were measured. The iodine adsorption values before and after activated carbon regeneration were 10 mg/g and 998 mg/g respectively, and the methylene blue adsorption values were respectively 1.5 mg/g and 153 mg/g, the waste mercury catalyst activated carbon recovered a higher adsorption capacity after regeneration and harmless treatment.
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