WO2016110081A1 - Acid waste gas treatment and resource utilization - Google Patents
Acid waste gas treatment and resource utilization Download PDFInfo
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- WO2016110081A1 WO2016110081A1 PCT/CN2015/084460 CN2015084460W WO2016110081A1 WO 2016110081 A1 WO2016110081 A1 WO 2016110081A1 CN 2015084460 W CN2015084460 W CN 2015084460W WO 2016110081 A1 WO2016110081 A1 WO 2016110081A1
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- WIPO (PCT)
- Prior art keywords
- waste gas
- liquid
- sodium salt
- sodium hydroxide
- spray
- Prior art date
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- 239000002912 waste gas Substances 0.000 title claims abstract description 40
- 239000002253 acid Substances 0.000 title claims abstract description 27
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 101
- 239000007788 liquid Substances 0.000 claims abstract description 61
- 239000007921 spray Substances 0.000 claims abstract description 38
- 238000010521 absorption reaction Methods 0.000 claims abstract description 35
- 159000000000 sodium salts Chemical class 0.000 claims abstract description 27
- 239000013078 crystal Substances 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 19
- 229920006395 saturated elastomer Polymers 0.000 claims abstract description 14
- 239000007787 solid Substances 0.000 claims abstract description 9
- 239000012670 alkaline solution Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 238000003756 stirring Methods 0.000 claims abstract description 4
- 239000007789 gas Substances 0.000 claims description 22
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 claims description 10
- 230000002378 acidificating effect Effects 0.000 claims description 7
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 5
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 5
- 239000012047 saturated solution Substances 0.000 claims description 5
- 238000002425 crystallisation Methods 0.000 claims description 3
- 230000008025 crystallization Effects 0.000 claims description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 238000012544 monitoring process Methods 0.000 abstract description 6
- 238000007599 discharging Methods 0.000 abstract description 3
- 230000007423 decrease Effects 0.000 abstract description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 11
- 238000000926 separation method Methods 0.000 description 9
- 229910052979 sodium sulfide Inorganic materials 0.000 description 9
- 239000002351 wastewater Substances 0.000 description 9
- 238000001556 precipitation Methods 0.000 description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 6
- 239000001632 sodium acetate Substances 0.000 description 6
- 235000017281 sodium acetate Nutrition 0.000 description 6
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 5
- 238000009776 industrial production Methods 0.000 description 4
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 235000010265 sodium sulphite Nutrition 0.000 description 2
- 230000001502 supplementing effect Effects 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000011555 saturated liquid Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/96—Regeneration, reactivation or recycling of reactants
Definitions
- the present invention relates to the field of industrial production, and particularly relates to the treatment and resource utilization of acid waste gas generated in industrial production, and belongs to the field of environmental protection.
- Acidic waste gas refers to an acid gas produced in industrial production.
- acid gas includes various exhaust gases such as acetic acid waste gas, hydrogen sulfide waste gas, and sulfur dioxide waste gas. If the acid gas cannot be treated with hydrazine, it will form acid rain after being emptied, causing serious natural disasters. Since the acid gas is acidic, it can be absorbed by the alkaline liquid to form a spray solution of the sodium salt solution, which is generally treated by the characteristics of the acid gas in the prior art.
- the amount of sodium salt solution formed by the acidic waste gas formed in industrial production is very large, so that the cost for environmentally friendly treatment will rise sharply, and it is difficult to promote the application in enterprises.
- some of the organic matter is vaporized during the evaporation process, thereby forming an organic waste gas, causing secondary exhaust gas pollution.
- the investment in evaporation crystallization equipment is high. Therefore, how to properly treat the acid gas spray liquid wastewater has become a major problem that restricts the normal operation of the acid waste gas treatment device.
- the inventors of the present invention have disclosed a new method for acid gas treatment and resource utilization, which includes the following steps, in view of the high operating cost and the tendency of secondary spray liquid wastewater pollution in the current acid gas treatment device. : [0005] (1) using sodium hydroxide solution as the absorption liquid, cyclically absorbing acid waste gas, and continuously monitoring the saturation degree of the absorption liquid with the saturated solubility of the formed sodium salt as a standard, and forming a saturated solution of the sodium salt, which will partially The spray liquid is discharged from the spray tower, and the alkaline solution formed in the step (3) is added to the spray tower to continue the exhaust gas spray absorption;
- step (3) The mixture obtained in the step (2) is subjected to solid-liquid separation, in which the solid portion is a sodium salt crystal, and the liquid portion is recycled to the step (1) to continue to be used as an absorption liquid.
- the present invention creatively provides an acid waste gas treatment and resource treatment process, using sodium hydroxide as an absorption liquid, by adding sodium hydroxide in a second excess, to obtain a sodium salt crystal, such as acetic acid, which meets market needs.
- a sodium salt crystal such as acetic acid
- Sodium, sodium sulfide, sodium sulfite or sodium chloride has great economic benefits.
- the invention creates a strong alkaline solution after the sodium salt is returned to the spray liquid, and can be completely returned to the exhaust gas spray tower without generating secondary waste water, and the spray liquid for acid waste gas treatment is realized. Zero discharge of wastewater has great market prospects.
- the solid-liquid separation may be a mild filtration, a centrifugal separation, or other commonly used solid-liquid separation means.
- step (2) the temperature is lowered to 5 to 10 °C.
- the concentration of the sodium hydroxide solution in the step (1) is 5% to 50 ⁇ 3 ⁇ 4 (w/w), and more preferably lO ⁇ SO ⁇ (w/w).
- the acid gas is acetic acid waste gas, hydrogen sulfide waste gas, sulfur dioxide waste gas or hydrogen chloride waste gas.
- the method is preferably applied to an acetic acid exhaust gas, a hydrogen sulfide exhaust gas, and a sulfur dioxide exhaust gas.
- step (3) Until there is no crystal precipitation, the mixture obtained in the step (2) is solid-liquid separated, and the separated solid is dried to obtain a commercial sodium salt crystal; the separation liquid is a high concentration sodium hydroxide solution. , Re-use to step (1) to achieve zero discharge of the spray liquid wastewater for acid waste gas absorption treatment.
- the mixture obtained in the step (2) is solid-liquid separated, and the separated solid is dried to obtain sodium sulfide crystals, and the recovery amount of the sodium sulfide is 80.5 g/L, and is recovered.
- the rate is 43.3%; the separation liquid is a high concentration sodium hydroxide absorption liquid, and is reused in the step (1).
- the mixture obtained in the step (2) is solid-liquid separated, and the separated solid is dried to obtain sodium sulfide crystals, and the amount of sodium sulfide recovered is 85.4 g/L, and recovered.
- the rate is 40.1%; the separation liquid is a high concentration sodium hydroxide absorption liquid, and is reused in the step (1).
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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Sustainable Development (AREA)
- Life Sciences & Earth Sciences (AREA)
- Treating Waste Gases (AREA)
- Gas Separation By Absorption (AREA)
Abstract
An acid waste gas treatment and resource utilization method comprises the following steps: (1) using a sodium hydroxide solution as an absorption liquid, absorbing acid waste gas in a circulated manner, constantly monitoring a saturation level of the absorption liquid based on formed saturated sodium salt solubility, when a saturated sodium salt solution is formed, discharging a part of a spray liquid from a spray tower, and adding a circulating alkaline solution formed in step (3) to the spray tower to continue to perform waste gas spray absorption; (2) adding a full dose of sodium hydroxide to a nearly saturated sodium salt spray liquid obtained in step (1), stirring well, and standing, to form crystals with a decrease of the temperature; and (3) separating the solid and liquid in the mixture obtained in step (2), the solid being sodium salt crystals, and the liquid entering step (1) and being used as the absorption liquid.
Description
酸性废气的治理及资源化利用 Acid waste gas treatment and resource utilization
技术领域 Technical field
[0001] 本发明涉及工业生产领域， 特别是涉及在工业生产中所产生的酸性废气的治理 及资源化利用， 属于环保治理领域。 [0001] The present invention relates to the field of industrial production, and particularly relates to the treatment and resource utilization of acid waste gas generated in industrial production, and belongs to the field of environmental protection.
背景技术 Background technique
[0002] 酸性废气是指在工业生产中所产生的酸性气体， 通常这类酸性气体包括醋酸废 气、 硫化氢废气、 以及二氧化硫废气等各类废气。 酸性气体如果不能及吋处理 ， 排空后就会形成酸雨， 造成严重的自然灾害。 酸性气体由于具有酸性因此可 以被碱性液体所吸收， 形成钠盐溶液的喷淋液， 目前现有技术中一般都是利用 酸性气体的这一特性进行处理。 [0002] Acidic waste gas refers to an acid gas produced in industrial production. Usually, such acid gas includes various exhaust gases such as acetic acid waste gas, hydrogen sulfide waste gas, and sulfur dioxide waste gas. If the acid gas cannot be treated with hydrazine, it will form acid rain after being emptied, causing serious natural disasters. Since the acid gas is acidic, it can be absorbed by the alkaline liquid to form a spray solution of the sodium salt solution, which is generally treated by the characteristics of the acid gas in the prior art.
技术问题 technical problem
[0003] 采用碱性液体吸收， 所形成的喷淋液由于不符合废水排放标准， 所以需要进一 步对其进行处理， 但由于喷淋液为超高含盐废水， 处理难度极大。 在研究之初 ， 我们想过采用蒸发结晶的方式， 但是， 很快我们就发现这一方式不适合工业 化应用。 主要原因有两个， 第一， 蒸发过程需要大量的热能， 按照目前热能成 本计算， 处理 1吨喷淋液的成本约为 120元、 得到 1吨钠盐的成本约需要 1万元的 成本。 而目前工业生产中所形成的酸性废气形成的钠盐溶液量非常大， 这样用 于环保处理的成本就会急剧升高， 很难在企业推广应用。 第二， 在蒸发过程中 部分有机物被气化， 从而形成有机物废气， 造成二次废气污染。 第三， 蒸发结 晶设备投资高。 因此， 如何合理的处理酸性气体喷淋液废水成为制约酸性废气 治理装置正常运行的重大难题。 [0003] With alkaline liquid absorption, the formed spray liquid does not meet the wastewater discharge standard, so it needs to be further processed. However, since the spray liquid is ultra-high salty wastewater, the treatment is extremely difficult. At the beginning of the study, we thought about the use of evaporative crystallization, but soon we found that this method is not suitable for industrial applications. There are two main reasons. First, the evaporation process requires a large amount of heat. According to the current heat energy cost, the cost of treating 1 ton of spray liquid is about 120 yuan, and the cost of getting 1 ton of sodium salt costs about 10,000 yuan. At present, the amount of sodium salt solution formed by the acidic waste gas formed in industrial production is very large, so that the cost for environmentally friendly treatment will rise sharply, and it is difficult to promote the application in enterprises. Second, some of the organic matter is vaporized during the evaporation process, thereby forming an organic waste gas, causing secondary exhaust gas pollution. Third, the investment in evaporation crystallization equipment is high. Therefore, how to properly treat the acid gas spray liquid wastewater has become a major problem that restricts the normal operation of the acid waste gas treatment device.
问题的解决方案 Problem solution
技术解决方案 Technical solution
[0004] 本发明的发明人针对目前酸性气体治理装置中运行成本高、 容易产生二次喷淋 液废水污染的问题， 公幵了一种全新的酸性气体治理及资源化利用方法， 包括 以下步骤：
[0005] (1) 以氢氧化钠溶液作为吸收液， 循环吸收酸性废气， 并不断以所形成的钠 盐饱和溶解度为标准， 监测吸收液的饱和程度， 当形成钠盐饱和溶液吋， 将部 分喷淋液排出喷淋塔， 并向喷淋塔内补充步骤 （3) 所形成的碱性溶液继续进行 废气喷淋吸收； [0004] The inventors of the present invention have disclosed a new method for acid gas treatment and resource utilization, which includes the following steps, in view of the high operating cost and the tendency of secondary spray liquid wastewater pollution in the current acid gas treatment device. : [0005] (1) using sodium hydroxide solution as the absorption liquid, cyclically absorbing acid waste gas, and continuously monitoring the saturation degree of the absorption liquid with the saturated solubility of the formed sodium salt as a standard, and forming a saturated solution of the sodium salt, which will partially The spray liquid is discharged from the spray tower, and the alkaline solution formed in the step (3) is added to the spray tower to continue the exhaust gas spray absorption;
[0006] (2) 向步骤 （1) 得到的钠盐饱和的喷淋液中投加足量氢氧化钠， 充分搅拌、 静置、 降温结晶； 由于氢氧化钠在加入过程中本身放热， 因此溶液温度升高， 当反应后， 随着温度逐渐下降恢复至室温， 有大量晶体析出， 但是优选地可以 进一步降温至 0~20°C。 [0006] (2) adding sufficient amount of sodium hydroxide to the sodium salt saturated spray liquid obtained in the step (1), stirring thoroughly, standing, and cooling the crystal; since the sodium hydroxide itself exotherms during the addition process, Therefore, the temperature of the solution rises, and after the reaction, as the temperature gradually decreases to return to room temperature, a large amount of crystals are precipitated, but it is preferable to further cool down to 0 to 20 °C.
[0007] (3) 将步骤 （2) 得到的混合物固液分离， 其中固体部分为钠盐晶体， 液体部 分循环进入步骤 （1) 继续作为吸收液使用。 (3) The mixture obtained in the step (2) is subjected to solid-liquid separation, in which the solid portion is a sodium salt crystal, and the liquid portion is recycled to the step (1) to continue to be used as an absorption liquid.
发明的有益效果 Advantageous effects of the invention
有益效果 Beneficial effect
[0008] 本发明创造性地给出了一种酸性废气的治理及资源化处理工艺， 以氢氧化钠作 为吸收液， 通过二次过量加入氢氧化钠， 得到符合市场需要的钠盐晶体， 譬如 醋酸钠、 硫化钠、 亚硫硫钠或氯化钠等， 具有极大地经济效益。 同吋， 本发明 创造在对喷淋液进行钠盐回后的喷淋液为强碱性溶液， 可全部回流到废气喷淋 塔， 不产生二次废水， 实现了酸性废气治理的喷淋液废水零排放， 具有极大的 市场推广前景。 [0008] The present invention creatively provides an acid waste gas treatment and resource treatment process, using sodium hydroxide as an absorption liquid, by adding sodium hydroxide in a second excess, to obtain a sodium salt crystal, such as acetic acid, which meets market needs. Sodium, sodium sulfide, sodium sulfite or sodium chloride has great economic benefits. At the same time, the invention creates a strong alkaline solution after the sodium salt is returned to the spray liquid, and can be completely returned to the exhaust gas spray tower without generating secondary waste water, and the spray liquid for acid waste gas treatment is realized. Zero discharge of wastewater has great market prospects.
对附图的简要说明 Brief description of the drawing
附图说明 DRAWINGS
[0009] 在此处键入附图说明描述段落。 [0009] The description paragraphs are entered here by way of a drawing.
实施该发明的最佳实施例 BEST MODE FOR CARRYING OUT THE INVENTION
本发明的最佳实施方式 BEST MODE FOR CARRYING OUT THE INVENTION
[0010] 其中固液分离可以是较为温和的过滤， 也可以是离心分离， 或者是其他常用的 固液分离手段。 [0010] wherein the solid-liquid separation may be a mild filtration, a centrifugal separation, or other commonly used solid-liquid separation means.
[0011] 优选地， 我们公幵步骤 （2) 中投加足量氢氧化钠是指每升钠盐饱和液中加入 5 0g~300g氢氧化钠。
[0012] 进一步地， 我们还优选步骤 （2) 中投加足量氢氧化钠是指每升钠盐饱和液中 加入 100g~200g氢氧化钠。 [0011] Preferably, we add a sufficient amount of sodium hydroxide in the step (2) to add 50 g to 300 g of sodium hydroxide per liter of the saturated salt of sodium salt. [0012] Further, we also preferably add a sufficient amount of sodium hydroxide in the step (2) to add 100 g to 200 g of sodium hydroxide per liter of the saturated sodium salt solution.
[0013] 优选地， 步骤 （2) 中降温至 5~10°C。 [0013] Preferably, in step (2), the temperature is lowered to 5 to 10 °C.
[0014] 我们还优选公幵了步骤 （1) 中氢氧化钠溶液的浓度为 5%~50<¾ (w/w) ， 更为 优选的是 lO^ SO^ (w/w) 。 [0014] We also preferably disclose that the concentration of the sodium hydroxide solution in the step (1) is 5% to 50 < 3⁄4 (w/w), and more preferably lO^SO^ (w/w).
[0015] 最后， 我们公幵所述酸性气体为醋酸废气、 硫化氢废气、 二氧化硫废气或氯化 氢废气。 本方法优选应用在醋酸废气、 硫化氢废气以及二氧化硫废气中。 [0015] Finally, we disclose that the acid gas is acetic acid waste gas, hydrogen sulfide waste gas, sulfur dioxide waste gas or hydrogen chloride waste gas. The method is preferably applied to an acetic acid exhaust gas, a hydrogen sulfide exhaust gas, and a sulfur dioxide exhaust gas.
本发明的实施方式 Embodiments of the invention
[0016] 为了更好的阐述本发明所公幵的技术方案， 下面我们结合具体实施例对本发明 进一步进行解释和说明。 [0016] In order to better explain the technical solutions disclosed in the present invention, the present invention will be further explained and illustrated in conjunction with specific embodiments.
[0017] 实施例 1 [0017] Embodiment 1
[0018] (1) 以 20<¾~30<¾(W/W)氢氧化钠溶液作为吸收液， 循环吸收酸性废气， 并不断 以酸性废气与氢氧化钠反应形成的钠盐饱和溶解度为标准监测吸收液的饱和程 度， 当形成接近饱和的钠盐溶液吋， 将喷淋液排出， 并向喷淋塔内补充步骤 （3 ) 所形成的碱性溶液继续进行废气喷淋吸收； [0018] (1) using 20<3⁄4~30<3⁄4( w / W ) sodium hydroxide solution as the absorption liquid, circulating acid waste gas, and continuously reacting the sodium salt saturated solubility formed by the reaction of acid waste gas with sodium hydroxide as standard Monitoring the saturation degree of the absorption liquid, when forming a nearly saturated sodium salt solution, discharging the spray liquid, and supplementing the spray solution with the alkaline solution formed in the step (3) to continue the exhaust gas spray absorption;
[0019] (2) 向步骤 （1) 得到的钠盐饱和液中按照 100g/L~200g/L的投加量投加氢氧 化钠， 充分搅拌， 静置， 温度下降得到大量的钠盐晶体析出； [0019] (2) To the sodium salt saturated liquid obtained in the step (1), sodium hydroxide is added in an amount of 100 g/L to 200 g/L, stirred well, allowed to stand, and the temperature is lowered to obtain a large amount of sodium salt crystals. Precipitate
[0020] (3) 至不再有晶体析出吋， 将步骤 （2) 得到的混合物固液分离， 分离后的固 体通过干燥处理， 得到商品钠盐晶体； 分离液为高浓度的氢氧化钠溶液， 重新 回用至步骤 （1) 中， 实现了酸性废气吸收治理的喷淋液废水零排放。 [0020] (3) Until there is no crystal precipitation, the mixture obtained in the step (2) is solid-liquid separated, and the separated solid is dried to obtain a commercial sodium salt crystal; the separation liquid is a high concentration sodium hydroxide solution. , Re-use to step (1) to achieve zero discharge of the spray liquid wastewater for acid waste gas absorption treatment.
[0021] 实施例 2 Embodiment 2
[0022] (1) 以 25%(w/w)氢氧化钠溶液作为吸收液， 循环吸收含醋酸废气， 并不断以 醋酸钠饱和溶解度为标准监测吸收液的饱和程度， 当形成保护醋酸钠溶液吋， 将喷淋液排出， 并向喷淋塔内补充步骤 （3) 所形成的碱性溶液继续进行废气喷 淋吸收； [0022] (1) using 25% (w / w) sodium hydroxide solution as an absorption liquid, circulating absorption of acetic acid-containing waste gas, and continuously monitoring the saturation degree of the absorption liquid with sodium acetate saturated solubility as a standard, when forming a protective sodium acetate solution吋, discharge the spray liquid, and add the alkaline solution formed in the step (3) to the spray tower to continue the exhaust gas spray absorption;
[0023] (2) 向步骤 （1) 得到的醋酸钠饱和液中按照 200g/L的投加量投加氢氧化钠， 充分搅拌， 静置， 降温至 10°C， 看到大量的醋酸钠晶体析出；
[0024] (3) 至不再有晶体析出吋， 将步骤 （2) 得到的混合物固液分离， 分离后的固 体通过干燥处理， 得到醋酸钠晶体， 醋酸钠回收量为 196g/L， 回收率为 42.2%; 分离液为高浓度的氢氧化钠吸收液， 回用至步骤 （1) 中。 [0023] (2) To the sodium acetate saturated solution obtained in the step (1), sodium hydroxide was added in an amount of 200 g/L, stirred well, allowed to stand, and the temperature was lowered to 10 ° C, and a large amount of sodium acetate was observed. Crystal precipitation; [0024] (3) until there is no crystal precipitation, the mixture obtained in the step (2) is solid-liquid separated, and the separated solid is dried to obtain sodium acetate crystals, and the recovery amount of sodium acetate is 196 g/L, and the recovery rate is It is 42.2%; the separation liquid is a high concentration sodium hydroxide absorption liquid, and is reused in the step (1).
[0025] 实施例 3 Embodiment 3
[0026] (1) 以 15% (w/w)氢氧化钠溶液作为吸收液， 循环吸收含硫化氢废气， 并不断 以硫化钠饱和溶解度为标准监测吸收液的饱和程度， 当形成饱和硫化钠溶液吋 ， 将喷淋液排出， 并向喷淋塔内补充步骤 （3) 所形成的碱性溶液继续进行废气 喷淋吸收； ； [0026] (1) using 15% (w / w) sodium hydroxide solution as an absorption liquid, circulating absorption of hydrogen sulfide-containing waste gas, and continuously monitoring the saturation degree of the absorption liquid with sodium sulfide saturation solubility as a standard, when forming saturated sodium sulfide Solution 吋, the spray liquid is discharged, and the alkaline solution formed in the step (3) is added to the spray tower to continue the exhaust gas spray absorption;
[0027] (2) 向步骤 （1) 得到的硫化钠饱和液中按照 150g/L的投加量投加氢氧化钠， 充分搅拌， 静置， 降温至 8°C， 看到大量的硫化钠晶体析出； [0027] (2) To the sodium sulfide saturated solution obtained in the step (1), sodium hydroxide was added in an amount of 150 g/L, stirred well, allowed to stand, and the temperature was lowered to 8 ° C, and a large amount of sodium sulfide was observed. Crystal precipitation;
[0028] (3) 至不再有晶体析出吋， 将步骤 （2) 得到的混合物固液分离， 分离后的固 体通过干燥处理， 得到硫化钠晶体， 硫化钠回收量为 80.5g/L， 回收率为 43.3%; 分离液为高浓度的氢氧化钠吸收液， 回用至步骤 （1) 中。 [0028] (3) Until there is no crystal precipitation, the mixture obtained in the step (2) is solid-liquid separated, and the separated solid is dried to obtain sodium sulfide crystals, and the recovery amount of the sodium sulfide is 80.5 g/L, and is recovered. The rate is 43.3%; the separation liquid is a high concentration sodium hydroxide absorption liquid, and is reused in the step (1).
[0029] 实施例 4 Embodiment 4
[0030] (1) 以 20% (w/w)氢氧化钠溶液作为吸收液， 循环吸收含二氧化硫废气， 并不 断以亚硫酸钠饱和溶解度为标准监测吸收液的饱和程度， 当形成饱和亚硫酸钠 溶液吋， 将喷淋液排出， 并向喷淋塔内补充步骤 （3) 所形成的碱性溶液继续进 行废气喷淋吸收； ； [0030] (1) using 20% (w / w) sodium hydroxide solution as an absorption liquid, circulating absorption of sulfur dioxide-containing waste gas, and continuously monitoring the saturation degree of the absorption liquid with sodium sulfite saturated solubility as a standard, when a saturated sodium sulfite solution is formed, Discharging the spray liquid, and supplementing the spray solution with the alkaline solution formed in step (3) to continue the exhaust gas spray absorption;
[0031] (2) 向步骤 （1) 得到的硫化钠饱和液中按照 100g/L的投加量投加氢氧化钠， 充分搅拌， 静置， 降温至 9°C， 看到大量的硫化钠晶体析出； (2) adding sodium hydroxide to the saturated sodium sulfide solution obtained in the step (1) at a dose of 100 g/L, stirring well, allowing to stand, and cooling to 9 ° C, and seeing a large amount of sodium sulfide. Crystal precipitation;
[0032] (3) 至不再有晶体析出吋， 将步骤 （2) 得到的混合物固液分离， 分离后的固 体通过干燥处理， 得到硫化钠晶体， 硫化钠回收量为 85.4g/L， 回收率为 40.1%; 分离液为高浓度的氢氧化钠吸收液， 回用至步骤 （1) 中。 [0032] (3) until there is no crystal precipitation, the mixture obtained in the step (2) is solid-liquid separated, and the separated solid is dried to obtain sodium sulfide crystals, and the amount of sodium sulfide recovered is 85.4 g/L, and recovered. The rate is 40.1%; the separation liquid is a high concentration sodium hydroxide absorption liquid, and is reused in the step (1).
工业实用性 Industrial applicability
[0033] 本研究与市场需求相结合， 重点解决酸性废气治理的问题， 并且将废气资源进 行回收利用。 以氢氧化钠作为吸收液， 通过二次过量加入氢氧化钠， 使吸收液 处于强碱状态， 对酸性废气的吸收效果大大提高， 同吋得到符合市场需要的钠 盐晶体， 可使废水的处理成本大大降低， 甚至可以带来一定的经济效益。 此外
， 本发明创造实现了酸性废气治理的喷淋液废水零排放。 在工业应用方面， 在 现有的碱液喷淋基础上， 只需增加一个加碱反应器及固液分离装置， 改造成本 低、 实用性强， 具有极大的市场推广前景。 [0033] This study, combined with market demand, focuses on solving the problem of acid waste gas treatment and recycling waste gas resources. With sodium hydroxide as the absorption liquid, the sodium hydroxide is added in a second excess, so that the absorption liquid is in a strong alkali state, the absorption effect on the acid waste gas is greatly improved, and the sodium salt crystal which meets the market demand is obtained, and the wastewater can be treated. The cost is greatly reduced, and it can even bring certain economic benefits. In addition The invention realizes zero discharge of the spray liquid wastewater which is treated by the acidic waste gas. In terms of industrial application, on the basis of the existing lye spray, it is only necessary to add an alkali-adding reactor and a solid-liquid separation device, which has low transformation cost and high practicability, and has great market promotion prospects.
序列表自由内容 Sequence table free content
在此处键入序列表自由内容描述段落。
Type the sequence table free content description paragraph here.
Claims
(1) 以氢氧化钠溶液作为吸收液， 循环吸收酸性废气， 并不断以 所形成的钠盐饱和溶解度为标准， 监测吸收液的饱和程度， 当形 成钠盐饱和溶液吋， 将部分喷淋液排出喷淋塔， 并向喷淋塔内补 充步骤 （3) 所形成的循环碱性溶液继续进行废气喷淋吸收；(1) Use sodium hydroxide solution as the absorption liquid to circulate the acidic waste gas, and constantly monitor the saturation degree of the absorption liquid based on the saturated solubility of the formed sodium salt. When a saturated sodium salt solution is formed, some of the spray liquid Discharge the spray tower, and replenish the circulating alkaline solution formed in step (3) into the spray tower to continue spraying and absorbing waste gas;
(2) 向步骤 （1) 得到的钠盐近饱和喷淋液中投加足量氢氧化钠 ， 充分搅拌， 静置， 随着温度下降产生结晶； (2) Add a sufficient amount of sodium hydroxide to the nearly saturated sodium salt spray liquid obtained in step (1), stir thoroughly, and let it stand for crystallization to occur as the temperature drops;
(3) 将步骤 （2) 得到的混合物固液分离， 其中固体部分为钠盐 晶体， 液体部分循环进入步骤 （1) 作为吸收液使用。 (3) Separate the mixture obtained in step (2) from solid to liquid, in which the solid part is sodium salt crystals, and the liquid part is recycled into step (1) for use as an absorption liquid.
根据权利要求 1所述的酸性废气的治理及资源化利用， 其特征在于 ： 步骤 （2) 中投加足量氢氧化钠是指每升钠盐饱和液中加入 50g~ 300g氢氧化钠。 The treatment and resource utilization of acid waste gas according to claim 1, characterized in that: adding a sufficient amount of sodium hydroxide in step (2) means adding 50g~300g sodium hydroxide per liter of sodium salt saturated solution.
根据权利要求 1所述的酸性废气的治理及资源化利用， 其特征在于 ： 步骤 （2) 中投加足量氢氧化钠是指每升钠盐饱和液中加入 100g ~200g氢氧化钠。 The treatment and resource utilization of acid waste gas according to claim 1, characterized in that: adding a sufficient amount of sodium hydroxide in step (2) means adding 100g ~ 200g sodium hydroxide per liter of sodium salt saturated solution.
根据权利要求 1所述的酸性废气的治理及资源化利用， 其特征在于 ： 步骤 （2) 中降温至 5~10°C。 The treatment and resource utilization of acid waste gas according to claim 1, characterized in that: in step (2), the temperature is lowered to 5~10°C.
根据权利要求 1~4中任意一项所述的酸性废气的治理及资源化利用 ， 其特征在于： 所述酸性气体为醋酸废气、 硫化氢废气、 二氧化 硫废气或氯化氢废气。
The treatment and resource utilization of acidic waste gas according to any one of claims 1 to 4, characterized in that: the acidic gas is acetic acid waste gas, hydrogen sulfide waste gas, sulfur dioxide waste gas or hydrogen chloride waste gas.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108273367A (en) * | 2018-04-04 | 2018-07-13 | 烟台国邦化工机械科技有限公司 | A kind of gas cleaning desalination process and system |
| CN112691528A (en) * | 2020-12-28 | 2021-04-23 | 厦门钨业股份有限公司 | Acid waste gas treatment system |
| CN114832463A (en) * | 2022-05-17 | 2022-08-02 | 四川东立科技股份有限公司 | Filter equipment is used in high-grade sulphuric acid production |
| CN114950078A (en) * | 2022-06-14 | 2022-08-30 | 扬州联博药业有限公司 | Waste gas treatment process in doxycycline hydrochloride production |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104524951B (en) * | 2015-01-09 | 2017-04-26 | 南京格洛特环境工程股份有限公司 | Acid waste gas treatment and resource utilization |
| CN104971609B (en) * | 2015-07-22 | 2017-04-05 | 南京格洛特环境工程股份有限公司 | A kind of Waste Hydrogen Fluoride Gas improvement and the method and apparatus of recycling |
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- 2015-07-20 WO PCT/CN2015/084460 patent/WO2016110081A1/en active Application Filing
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| JP2005305414A (en) * | 2004-10-15 | 2005-11-04 | Sumitomo Chemical Co Ltd | Detoxifying method for chlorine gas |
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| CN108273367A (en) * | 2018-04-04 | 2018-07-13 | 烟台国邦化工机械科技有限公司 | A kind of gas cleaning desalination process and system |
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| CN114950078A (en) * | 2022-06-14 | 2022-08-30 | 扬州联博药业有限公司 | Waste gas treatment process in doxycycline hydrochloride production |
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| SG11201706471QA (en) | 2017-09-28 |
| CN104524951A (en) | 2015-04-22 |
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