CN116040827A - Method for treating catalytic cracking flue gas desulfurization wastewater - Google Patents
Method for treating catalytic cracking flue gas desulfurization wastewater Download PDFInfo
- Publication number
- CN116040827A CN116040827A CN202111263222.9A CN202111263222A CN116040827A CN 116040827 A CN116040827 A CN 116040827A CN 202111263222 A CN202111263222 A CN 202111263222A CN 116040827 A CN116040827 A CN 116040827A
- Authority
- CN
- China
- Prior art keywords
- adsorbent
- nickel
- vanadium
- wastewater
- flue gas
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000002351 wastewater Substances 0.000 title claims abstract description 72
- 238000000034 method Methods 0.000 title claims abstract description 49
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 239000003546 flue gas Substances 0.000 title claims abstract description 43
- 238000004523 catalytic cracking Methods 0.000 title claims abstract description 39
- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 38
- 230000023556 desulfurization Effects 0.000 title claims abstract description 38
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 177
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 85
- 239000003463 adsorbent Substances 0.000 claims abstract description 83
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 80
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 80
- 238000003795 desorption Methods 0.000 claims abstract description 65
- 238000001179 sorption measurement Methods 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 15
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004064 recycling Methods 0.000 claims abstract description 8
- 238000000926 separation method Methods 0.000 claims abstract description 8
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 239000000463 material Substances 0.000 claims abstract description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 36
- 238000001914 filtration Methods 0.000 claims description 26
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 16
- 229960004887 ferric hydroxide Drugs 0.000 claims description 15
- IEECXTSVVFWGSE-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Fe+3] IEECXTSVVFWGSE-UHFFFAOYSA-M 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000003513 alkali Substances 0.000 claims description 9
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 7
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 7
- 235000011152 sodium sulphate Nutrition 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 0.000 claims description 5
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000005708 Sodium hypochlorite Substances 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000007670 refining Methods 0.000 claims description 3
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 claims description 3
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 claims description 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 150000007522 mineralic acids Chemical class 0.000 claims description 2
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 2
- 239000002585 base Substances 0.000 claims 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 3
- 238000011084 recovery Methods 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- 229920006395 saturated elastomer Polymers 0.000 abstract description 2
- 238000001514 detection method Methods 0.000 description 12
- 238000005342 ion exchange Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 238000002336 sorption--desorption measurement Methods 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- PXLIDIMHPNPGMH-UHFFFAOYSA-N sodium chromate Chemical compound [Na+].[Na+].[O-][Cr]([O-])(=O)=O PXLIDIMHPNPGMH-UHFFFAOYSA-N 0.000 description 3
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 3
- 229910052815 sulfur oxide Inorganic materials 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000003957 anion exchange resin Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 230000002308 calcification Effects 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000003729 cation exchange resin Substances 0.000 description 1
- 229940023913 cation exchange resins Drugs 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 239000011268 mixed slurry Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005201 scrubbing Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- -1 vanadate ions Chemical class 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000005200 wet scrubbing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/38—Treatment of water, waste water, or sewage by centrifugal separation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2303/00—Specific treatment goals
- C02F2303/16—Regeneration of sorbents, filters
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to a method for treating catalytic cracking flue gas desulfurization wastewater, which comprises the steps of adjusting the pH value of the catalytic cracking flue gas desulfurization wastewater to 2-14, and adding an iron-based adsorbent for treatment; carrying out solid-liquid separation on the treated material to obtain an adsorbent after adsorption and wastewater after vanadium and nickel removal; and (3) carrying out stepwise desorption on the adsorbent after adsorption to obtain vanadium-containing solution, nickel-containing solution and regenerated adsorbent, and returning the regenerated adsorbent to the adsorption process for recycling. According to the invention, specific adsorbents are selected according to the water quality characteristics of the catalytic cracking flue gas desulfurization wastewater, vanadium and nickel in the wastewater can be simultaneously adsorbed and removed, and the saturated adsorbents can be recycled after regeneration, so that the high-efficiency recovery of vanadium and nickel is realized.
Description
Technical Field
The invention belongs to the technical field of water pollution treatment, and particularly relates to a method for treating catalytic cracking flue gas desulfurization wastewater.
Background
A large amount of sulfur-containing flue gas is generated in the petroleum catalytic cracking process, and problems caused by the discharge of the flue gas have attracted serious attention in various countries. The pollutants in the catalytic cracking flue gas mainly comprise sulfur oxides and smoke dust particles, the emission of the sulfur oxides is limited in China, and a series of local standards and national standards are established. For the treatment of sulfur oxides, wet scrubbing is generally used, i.e. the flue gas is scrubbed with a scrubbing solution containing alkaline substances, and the sulfur-containing acid gases therein are absorbed and converted into sulfates. However, since the petroleum contains elements such as vanadium and nickel, the elements can enter the flue gas in the petroleum refining process, when the flue gas is desulfurized, the produced flue gas desulfurization wastewater often contains toxic and harmful heavy metal substances such as vanadium and nickel, and the content of the heavy metal substances is in an excessive risk, so that deep removal is needed.
CN101113062A is treated by ion exchange method to treat vanadium-containing wastewater to 1mgL -1 In the following, the national emission standard is reached. CN103693711A is treated with weak acid ion exchange fiber to obtain nickel containing effluent with nickel content lower than 0.5mg L -1 And (5) discharging after reaching the standard. CN107188326A is treated by hydrogen peroxide-ion exchange combination to obtain nickel-containing wastewater with nickel content lower than 0.1mg L -1 Is lower than the national emission standard. However, the above patents select anion exchange or cation exchange methods for the form of ion existence in the wastewater, and only a certain type of heavy metal ions can be removed in a targeted manner, because vanadium and nickel exist in the wastewater in the form of anions and cations respectively, if the ion exchange method is adopted to treat wastewater containing vanadium and nickel, anion exchange resins and cation exchange resins need to be used in combination, so that the complexity of the process and operation is increased significantly. Meanwhile, the ion exchange method has more severe requirements on the pH of the solution, the pH required for removing different ions is different, and the treatment cost and the operation difficulty are increased by using the pH regulator and the pH regulator of the wastewater. In addition, if a large amount of sodium ions and sulfate ions exist in the wastewater, the ion exchange method is difficult to obtain a good removal effect.
Li Hualin et al (mesoporous Cr (OH) 3 Is prepared from the composition and its adsorption performance to V ions]Chemical engineering journal 2016, v.67 (12): 5283-5290.) mesoporous Cr (OH) was used 3 The vanadium-containing wastewater is adsorbed, so that the vanadium concentration in the wastewater can be reduced to 1mg L -1 Hereinafter, however, since the adsorbent used contains heavy metalsCr may introduce new Cr contaminants during the process.
CN104085949a discloses a method for removing vanadium from sodium chromate leaching solution by ferric hydroxide adsorption, which comprises the following steps: adding ferric hydroxide into the sodium chromate leaching solution with pH value of 2-14 to perform desorption reaction, wherein the ferric hydroxide and vanadium (in V 2 O 5 Calculated as mass ratio) is 2:1 to 15:1, the reaction temperature is 30-100 ℃ and the reaction time is 5-120min; filtering and separating the obtained mixed slurry at 30-100deg.C to obtain vanadium-containing residue and vanadium-removed liquid (V) 2 O 5 Meter) is less than 0.08g/L; the desorption and desorption of the vanadium-containing slag can be realized after the treatment of dilute alkali solution, the ferric hydroxide after the desorption returns to the vanadium removal stage for recycling, and the vanadium-containing liquid can be used for extracting vanadium and obtaining vanadium products by adopting the traditional methods of calcification, ammonium precipitation or neutralization and the like; the method can be operated only under normal pressure, is easy to carry out, has good safety, high vanadium removal rate and recycling ferric hydroxide. However, the patent realizes the removal of vanadium in sodium chromate solution, has stricter requirements on residual concentration of heavy metals for catalytic cracking flue gas desulfurization wastewater, and has to be further improved because vanadium, nickel and a large amount of sodium sulfate are simultaneously present in the wastewater.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for treating catalytic cracking flue gas desulfurization wastewater. According to the invention, specific adsorbents are selected according to the water quality characteristics of the catalytic cracking flue gas desulfurization wastewater, vanadium and nickel in the wastewater can be simultaneously adsorbed and removed, and the saturated adsorbents can be recycled after regeneration, so that the high-efficiency recovery of vanadium and nickel is realized.
The invention provides a method for treating catalytic cracking flue gas desulfurization wastewater, which comprises the following steps:
(1) Adjusting the pH value of the catalytic cracking flue gas desulfurization wastewater to 2-14, and adding an iron-based adsorbent for treatment;
(2) Carrying out solid-liquid separation on the treated material to obtain an adsorbent after adsorption and wastewater after vanadium and nickel removal;
(3) And (3) carrying out stepwise desorption on the adsorbent after adsorption to obtain vanadium-containing solution, nickel-containing solution and regenerated adsorbent, and returning the regenerated adsorbent to the adsorption process for recycling.
In the invention, the catalytic cracking flue gas desulfurization wastewater in the step (1) refers to wastewater containing vanadium, nickel and sodium sulfate, which is generated in the desulfurization procedure of catalytic cracking flue gas generated in the oil refining process, wherein the vanadium content is 1-5mgL -1 Nickel content of 1-5mgL -1 Sodium sulfate content of 10000-50000mgL -1 。
In the invention, the pH value of the catalytic cracking flue gas desulfurization wastewater in the step (1) is adjusted to 2-14, and any one of inorganic acid or inorganic alkali, preferably sulfuric acid or sodium hydroxide, is adopted.
In the present invention, the iron-based adsorbent in the step (1) is at least one of ferric hydroxide, and the like.
In the present invention, the iron-based adsorbent in the step (1) is added in an amount of 0.01 to 50. 50g L -1 Preferably 0.25-5g L -1 The method comprises the steps of carrying out a first treatment on the surface of the The adsorption temperature is 0-60 ℃, preferably 1-40 ℃, and the adsorption time is 0.1-10h, preferably 0.2-2h.
In the invention, further, the step (1) is to add an oxidant for pretreatment of the catalytic cracking flue gas desulfurization wastewater, wherein the oxidant is at least one of hydrogen peroxide, persulfate, sodium chlorate or sodium hypochlorite, and the addition amount is 0.01-0.5mg L -1 。
In the invention, the solid-liquid separation of the material treated in the step (1) in the step (2) can be carried out by adopting a solid-liquid separation mode conventionally used in the field, such as filtration, centrifugation and the like, wherein the temperature of the solid-liquid separation is 0-60 ℃, preferably 1-40 ℃. And obtaining the adsorbent after adsorption and the catalytic cracking flue gas desulfurization wastewater after vanadium and nickel removal.
In the invention, the adsorbent obtained in the step (2) after adsorption is desorbed to obtain vanadium-containing solution, nickel-containing solution and regenerated adsorbent. The desorption is preferably carried out by the following method: the method comprises two steps, wherein the adsorbent is added into a strong alkali solution for desorption, and the mass concentration of the strong alkali solution is 1% -20%; the strong alkali is at least one of inorganic strong alkali such as NaOH, KOH and the like, and NaOH is preferred; the desorption temperature is 0-70 ℃, preferably 10-60 ℃; the desorption time is 0.1 to 10 hours, preferably 0.2 to 2 hours. After the desorption is completed, filtering to obtain vanadium-containing solution and nickel-containing adsorbent; and in the second step, adding the nickel-containing adsorbent into an ammonia water solution for reaction, wherein the mass fraction of the ammonia water solution is 1% -20%, the reaction temperature is 0-60 ℃, and the reaction time is 0.1-10h, preferably 0.2-2h. The method comprises the steps of carrying out a first treatment on the surface of the The nickel-containing solution and the regenerated adsorbent are obtained after filtration, and the regenerated adsorbent can be returned to the adsorption process for recycling.
In the invention, the vanadium-containing solution and the nickel-containing solution obtained in the step (3) are respectively used for producing corresponding vanadium and nickel products by a conventional method.
Compared with the prior art, the invention has the following beneficial effects:
(1) Aiming at the water quality characteristics of the catalytic cracking flue gas desulfurization wastewater, the adsorbent adopted by the invention can adsorb and remove vanadium and nickel in the catalytic cracking flue gas desulfurization wastewater, vanadate ions in the wastewater are adsorbed on the surface of the adsorbent in a double coordination surface complexing mode, and the adsorbent is negatively charged after adsorption, so that positively charged Ni can be adsorbed 2+ The ion realizes the high-efficiency adsorption and removal of vanadium and nickel, and the concentration of vanadium and nickel in the wastewater after adsorption can be reduced to be lower than 0.1mg L -1 。
(2) The invention can further improve the nickel removal effect by adding a proper amount of oxidant to pretreat the catalytic cracking flue gas desulfurization wastewater.
(3) The vanadium and nickel on the adsorbent after adsorption can be desorbed step by step to obtain the solution containing vanadium and nickel respectively, which is beneficial to recycling the vanadium and nickel. After the adsorbent is regenerated, the adsorbent can be recycled, the adsorption cost is low, and no new solid waste is generated.
(4) The invention has the characteristics of wide pH application range, no introduction of harmful substances, good treatment effect, low cost, simple operation and the like.
Drawings
FIG. 1 is a process flow diagram of the catalytic cracking flue gas desulfurization wastewater treatment method of the present invention.
Detailed Description
The catalytic cracking flue gas desulfurization wastewater treatment method and the effect thereof according to the present invention are further described below by way of examples. The embodiment is 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 to the following embodiment.
The experimental methods in the following examples, unless otherwise specified, are all conventional in the art. The experimental materials used in the examples described below were purchased from biochemical reagent stores unless otherwise specified.
The catalytic cracking flue gas desulfurization wastewater adopted in the embodiment of the invention is wastewater containing vanadium, nickel and sodium sulfate, wherein the initial concentration of the vanadium and the nickel in the wastewater is 3.6mg L respectively, and the wastewater is produced in the desulfurization procedure of catalytic cracking flue gas generated in the oil refining process -1 And 1.65mg L -1 Sodium sulfate content of 50000mgL -1 。
In the invention, ICP-MS is adopted to measure the vanadium and nickel contents in the wastewater before and after adsorption.
Example 1
The pH value of the catalytic cracking flue gas desulfurization wastewater is adjusted to 2, ferric hydroxide is added into the wastewater, and the addition amount is 5g L -1 The adsorption temperature is 30 ℃, the adsorption time is 2 hours, the treated wastewater and the adsorbent after adsorption are obtained after filtration, and the removal rates of vanadium and nickel are respectively 99.97% and 95.75% after detection and calculation.
And (3) desorbing the adsorbent after adsorption in two steps, wherein the mass concentration of the adsorbent is 1% in NaOH and solution, the desorption temperature is 0 ℃, and the desorption time is 0.2h. After the desorption is completed, filtering to obtain vanadium-containing solution and nickel-containing adsorbent; and secondly, adding the nickel-containing adsorbent into an ammonia water solution for reaction, wherein the mass fraction of the ammonia water solution is 1%, the desorption temperature is 30 ℃, and the desorption time is 0.2h. After filtration, a nickel-containing solution and a regenerated adsorbent are obtained, the content of vanadium and nickel in the desorption liquid is measured, and the calculated desorption rates of the vanadium and the nickel can reach 90.3% and 91.1% respectively.
Example 2
The pH value of the catalytic cracking flue gas desulfurization wastewater is adjusted to 7, ferric hydroxide is added into the wastewater, and the addition amount is 5g L -1 The adsorption temperature is 30 ℃, the adsorption time is 2 hours, the treated wastewater and the adsorbent after adsorption are obtained after filtration, and the detection and calculation are carried outThe removal rates of vanadium and nickel are 99.97% and 96.93% respectively.
And (3) carrying out stepwise desorption on the adsorbent after adsorption, wherein the mass concentration of the adsorbent is 5% in NaOH and solution, the desorption temperature is 30 ℃, and the desorption time is 2 hours. And after the desorption is finished, filtering to obtain vanadium-containing solution and nickel-containing adsorbent. And secondly, adding the nickel-containing adsorbent into an ammonia water solution for reaction, wherein the mass fraction of the ammonia water solution is 5%, the desorption temperature is 30 ℃, and the desorption time is 2 hours. After filtration, a nickel-containing solution and a regenerated adsorbent are obtained, the content of vanadium and nickel in the desorption liquid is measured, and the calculated desorption rates of the vanadium and the nickel can reach 97.3% and 97.1% respectively.
Example 3
The pH value of the catalytic cracking flue gas desulfurization wastewater is adjusted to 14, ferric hydroxide is added into the wastewater, and the addition amount is 5g L -1 The adsorption temperature is 30 ℃, the adsorption time is 2 hours, the treated wastewater and the adsorbent after adsorption are obtained after filtration, and the removal rates of vanadium and nickel are respectively 99.95% and 95.95% after detection and calculation.
The adsorbent after adsorption is desorbed step by step, firstly, the adsorbent is added into NaOH and solution, and the mass concentration is 20%; the desorption temperature is 60 ℃ and the desorption time is 2 hours. And after the desorption is finished, filtering to obtain vanadium-containing solution and nickel-containing adsorbent. And secondly, adding the nickel-containing adsorbent into an ammonia water solution for reaction, wherein the mass fraction of the ammonia water solution is 20%, the desorption temperature is 60 ℃, and the desorption time is 2 hours. After filtration, a nickel-containing solution and a regenerated adsorbent are obtained, the content of vanadium and nickel in the desorption liquid is measured, and the calculated desorption rates of the vanadium and the nickel can reach 97.9% and 98.2% respectively.
Example 4
The pH value of the catalytic cracking flue gas desulfurization wastewater is adjusted to 7, ferric hydroxide is added into the wastewater, and the addition amount is 0.2g L -1 The adsorption temperature is 60 ℃, the adsorption time is 0.5h, the treated wastewater and the adsorbed ferric hydroxide are obtained after filtration, the treated wastewater and the adsorbed adsorbent are obtained after filtration, and the removal rates of vanadium and nickel are 97.65% and 93.68% respectively through detection and calculation.
And (3) carrying out stepwise desorption on the adsorbent after adsorption, wherein the mass concentration of the adsorbent is 5% in NaOH and solution, the desorption temperature is 30 ℃, and the desorption time is 2 hours. And after the desorption is finished, filtering to obtain vanadium-containing solution and nickel-containing adsorbent. And secondly, adding the nickel-containing adsorbent into an ammonia water solution for reaction, wherein the mass fraction of the ammonia water solution is 5%, the desorption temperature is 30 ℃, and the desorption time is 2 hours. After filtration, a nickel-containing solution and a regenerated adsorbent are obtained, the content of vanadium and nickel in the desorption liquid is measured, and the calculated desorption rates of the vanadium and the nickel can reach 96.3% and 95.7% respectively.
Example 5
The pH value of the catalytic cracking flue gas desulfurization wastewater is adjusted to 7, ferric hydroxide is added into the wastewater, and the addition amount is 50g L -1 The adsorption temperature is 0 ℃, the adsorption time is 6 hours, the treated wastewater and the adsorbent after adsorption are obtained after filtration, and the removal rates of vanadium and nickel are respectively 99.98% and 95.96% after detection and calculation.
And (3) carrying out stepwise desorption on the adsorbent after adsorption, wherein the mass concentration of the adsorbent is 5% in NaOH and solution, the desorption temperature is 30 ℃, and the desorption time is 2 hours. And after the desorption is finished, filtering to obtain vanadium-containing solution and nickel-containing adsorbent. And secondly, adding the nickel-containing adsorbent into an ammonia water solution for reaction, wherein the mass fraction of the ammonia water solution is 5%, the desorption temperature is 30 ℃, and the desorption time is 2 hours. After filtration, a nickel-containing solution and a regenerated adsorbent are obtained, the content of vanadium and nickel in the desorption liquid is measured, and the calculated desorption rates of the vanadium and the nickel can reach 97.1% and 92.9% respectively.
Example 6
The pH value of the catalytic cracking flue gas desulfurization wastewater is adjusted to 7, ferric hydroxide is added into the wastewater, and the addition amount is 5g L -1 The adsorption temperature is 30 ℃, the adsorption time is 2 hours, the treated wastewater and the adsorbent after adsorption are obtained after filtration, and the removal rates of vanadium and nickel are respectively 99.96% and 95.90% after detection and calculation.
And (3) carrying out stepwise desorption on the adsorbent after adsorption, wherein the mass concentration of the adsorbent is 5% in NaOH and solution, the desorption temperature is 30 ℃, and the desorption time is 2 hours. And after the desorption is finished, filtering to obtain vanadium-containing solution and nickel-containing adsorbent. And secondly, adding the nickel-containing adsorbent into an ammonia water solution for reaction, wherein the mass fraction of the ammonia water solution is 5%, the desorption temperature is 30 ℃, and the desorption time is 2 hours. After filtration, a nickel-containing solution and a regenerated adsorbent are obtained, the content of vanadium and nickel in the desorption liquid is measured, and the calculated desorption rates of the vanadium and the nickel can reach 96.7% and 97.0% respectively.
Example 7
The adsorption-desorption cycle was performed under the conditions in example 2, and the adsorbent and the desorption cycle were used. After the detection and calculation, the removal rate of vanadium and nickel can still reach 98.78 percent and 94.71 percent after the adsorption-desorption cycle is repeated for 6 times, the desorption rates of vanadium and nickel are respectively 96.1 percent and 95.7 percent, and the vanadium and nickel can be desorbed in steps and recycled respectively.
Example 8
The adsorption-desorption cycle was performed under the conditions in example 6, and the adsorbent and the desorption cycle were used. After detection and calculation, after 6 times of repeated adsorption-desorption cycles, the removal rate of vanadium and nickel can still reach 99.90 percent and 94.21 percent, and the vanadium and the nickel can be desorbed step by step and recycled respectively.
Example 9
The difference from example 2 is that: step (1) adding sodium persulfate to pretreat the catalytic cracking flue gas desulfurization wastewater, wherein the addition amount is 0.05mg L -1 . The removal rates of vanadium and nickel are 99.76% and 99.1% respectively through detection calculation.
Example 10
The difference from example 2 is that: step (1) adding sodium hypochlorite to pretreat the catalytic cracking flue gas desulfurization wastewater, wherein the addition amount is 0.05mg L -1 . The removal rates of vanadium and nickel are respectively 99.55 percent and 99.88 percent through detection and calculation.
Comparative example 1
The difference from example 2 is that: wastewater from this application was treated using the method described in CN104085949 a. The removal rates of vanadium and nickel are 23.04% and 10.17% respectively through detection and calculation.
Comparative example 2
The difference from example 2 is that: ferric oxide is used as an adsorbent. The removal rates of vanadium and nickel are 11.05% and 5.71% respectively through detection calculation.
Claims (13)
1. The method for treating the catalytic cracking flue gas desulfurization wastewater is characterized by comprising the following steps of: (1) Adjusting the pH value of the catalytic cracking flue gas desulfurization wastewater to 2-14, and adding an iron-based adsorbent for treatment; (2) Carrying out solid-liquid separation on the treated material to obtain an adsorbent after adsorption and wastewater after vanadium and nickel removal; (3) And (3) carrying out stepwise desorption on the adsorbent after adsorption to obtain vanadium-containing solution, nickel-containing solution and regenerated adsorbent, and returning the regenerated adsorbent to the adsorption process for recycling.
2. The method according to claim 1, characterized in that: the desulfurization wastewater of the catalytic cracking flue gas generated in the step (1) refers to wastewater containing vanadium, nickel and sodium sulfate, wherein the wastewater contains 1-5mg L of vanadium, and the wastewater is generated in the desulfurization procedure of the catalytic cracking flue gas generated in the oil refining process -1 The nickel content is 1-5mg L -1 Sodium sulfate content of 10000-50000mg L -1 。
3. The method according to claim 1 or 2, characterized in that: and (3) adjusting the pH value of the catalytic cracking flue gas desulfurization wastewater to 2-14 in the step (1), wherein any one of inorganic acid or inorganic alkali, preferably sulfuric acid or sodium hydroxide, is adopted.
4. The method according to claim 1, characterized in that: the iron-based adsorbent in the step (1) is at least one of ferric hydroxide and ferric hydroxide.
5. The method according to claim 1 or 4, characterized in that: the addition amount of the iron-based adsorbent in the step (1) is 0.01-50g L -1 Preferably 0.25-5g L -1 。
6. The method according to claim 1 or 4, characterized in that: the adsorption temperature is 0-60 ℃, preferably 1-40 ℃, and the adsorption time is 0.1-10h, preferably 0.2-2h.
7. The method according to claim 1, characterized in that: step (1) adding oxidant to the catalytic cracking smokePretreating gas desulfurization wastewater, wherein the oxidant is at least one of hydrogen peroxide, persulfate, sodium chlorate or sodium hypochlorite, and the addition amount is 0.01-0.5mg L -1 。
8. The method according to claim 1, characterized in that: and (2) carrying out solid-liquid separation on the material treated in the step (1), wherein the separation temperature is 0-60 ℃, preferably 1-40 ℃.
9. The method according to claim 1, characterized in that: and (3) desorbing by adopting the following method: the method comprises two steps, wherein the adsorbent is added into a strong alkali solution for desorption, and the mass concentration of the strong alkali solution is 1% -20%; after the desorption is completed, filtering to obtain vanadium-containing solution and nickel-containing adsorbent; and secondly, adding the nickel-containing adsorbent into an ammonia water solution for reaction, wherein the mass fraction of the ammonia water solution is 1% -20%, and filtering to obtain the nickel-containing solution and the regenerated adsorbent.
10. The method according to claim 9, wherein: the strong base in the first step is at least one of NaOH and KOH inorganic strong base, preferably NaOH.
11. The method according to claim 9 or 10, characterized in that: the desorption temperature in the first step is 0-70 ℃, preferably 10-60 ℃; the desorption time is 0.1 to 10 hours, preferably 0.2 to 2 hours.
12. The method according to claim 9, wherein: the reaction temperature of the second step is 0-60 ℃, and the reaction time is 0.1-10h, preferably 0.2-2h.
13. The method according to claim 9, wherein: and (3) filtering in the second step to obtain regenerated adsorbent, and returning the regenerated adsorbent to the adsorption process for recycling.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111263222.9A CN116040827A (en) | 2021-10-28 | 2021-10-28 | Method for treating catalytic cracking flue gas desulfurization wastewater |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111263222.9A CN116040827A (en) | 2021-10-28 | 2021-10-28 | Method for treating catalytic cracking flue gas desulfurization wastewater |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116040827A true CN116040827A (en) | 2023-05-02 |
Family
ID=86130157
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111263222.9A Pending CN116040827A (en) | 2021-10-28 | 2021-10-28 | Method for treating catalytic cracking flue gas desulfurization wastewater |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116040827A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002256354A (en) * | 2001-03-06 | 2002-09-11 | Chiyoda Corp | Method for separating and recovering vanadium |
| US20080197081A1 (en) * | 2005-04-25 | 2008-08-21 | The Regents Of The University Of California | Compositions and Methods For Removing Arsenic in Water |
| CN104085949A (en) * | 2014-06-24 | 2014-10-08 | 中国科学院过程工程研究所 | Method for removing vanadium from sodium chromate leaching solution by ferric hydroxide adsorption |
| CN104437345A (en) * | 2014-11-15 | 2015-03-25 | 中国科学院过程工程研究所 | Solvent-thermal preparation method of porous ferroferric oxide adsorption material |
| CN108249623A (en) * | 2018-02-07 | 2018-07-06 | 湖南净源环境工程有限公司 | A kind of Ni-containing Plating Wastewater treatment process and system |
| CN108675498A (en) * | 2018-05-25 | 2018-10-19 | 中国科学院过程工程研究所 | A kind of method of bone coal acid waste water recycling |
| CN109336232A (en) * | 2018-11-20 | 2019-02-15 | 常州工学院 | A method of nickel-containing waste water is handled using recycling silicon bath soil |
| CN112941330A (en) * | 2021-01-27 | 2021-06-11 | 长兴旗滨玻璃有限公司 | Petroleum coke smoke dust treatment method |
-
2021
- 2021-10-28 CN CN202111263222.9A patent/CN116040827A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2002256354A (en) * | 2001-03-06 | 2002-09-11 | Chiyoda Corp | Method for separating and recovering vanadium |
| US20080197081A1 (en) * | 2005-04-25 | 2008-08-21 | The Regents Of The University Of California | Compositions and Methods For Removing Arsenic in Water |
| CN104085949A (en) * | 2014-06-24 | 2014-10-08 | 中国科学院过程工程研究所 | Method for removing vanadium from sodium chromate leaching solution by ferric hydroxide adsorption |
| CN104437345A (en) * | 2014-11-15 | 2015-03-25 | 中国科学院过程工程研究所 | Solvent-thermal preparation method of porous ferroferric oxide adsorption material |
| CN108249623A (en) * | 2018-02-07 | 2018-07-06 | 湖南净源环境工程有限公司 | A kind of Ni-containing Plating Wastewater treatment process and system |
| CN108675498A (en) * | 2018-05-25 | 2018-10-19 | 中国科学院过程工程研究所 | A kind of method of bone coal acid waste water recycling |
| CN109336232A (en) * | 2018-11-20 | 2019-02-15 | 常州工学院 | A method of nickel-containing waste water is handled using recycling silicon bath soil |
| CN112941330A (en) * | 2021-01-27 | 2021-06-11 | 长兴旗滨玻璃有限公司 | Petroleum coke smoke dust treatment method |
Non-Patent Citations (1)
| Title |
|---|
| 罗南;刘波;李国良;何晋秋;: "活性氢氧化铁处理含钒(Ⅴ)废水的研究", 四川环境, vol. 08, no. 01, 31 December 1998 (1998-12-31), pages 39 - 48 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101538652B (en) | Method for separating and recovering vanadium and chrome from vanadium and chrome-containing waste | |
| CN105289261B (en) | It is a kind of to be used for the cleaning solution that mercury elutes in mercury fume and the method that mercury is reclaimed from mercury fume | |
| CN108002580B (en) | Method for treating acidic flue gas washing wastewater and application thereof | |
| CN103301819B (en) | Preparation method of nano adsorbent for removing heavy metals in wastewater | |
| CN110129561B (en) | Method for removing fluorine in lepidolite neutral leaching solution by using modified bentonite adsorbent | |
| CN104692579A (en) | Advanced recycling method for wastewater generated in making acid by using smelting flue gas | |
| CN105198030A (en) | Method for removing chloride ions in water through garlic waste | |
| CN109850935B (en) | Method for preparing thallium chloride by using thallium-containing acidic wastewater of smelting plant as raw material | |
| CN111252875A (en) | Treatment process of heavy metal-containing wastewater | |
| CN110605108A (en) | Method for regenerating desulfurization and denitrification waste active carbon | |
| CN113058663A (en) | Detoxification regeneration method of ion exchange resin for uranium adsorption | |
| CN116040827A (en) | Method for treating catalytic cracking flue gas desulfurization wastewater | |
| CN107381705B (en) | Method for separating and recovering multiple cationic heavy metals in water through phase change regulation | |
| CN107473319B (en) | Method for recovering cationic heavy metals in water through phase change regulation | |
| CN110846510A (en) | Method for efficiently and selectively adsorbing and recovering rhenium and mercury from copper smelting multi-element mixed waste acid | |
| CN109455761A (en) | A method of removing vanadium from molybdate solution | |
| CN115571948A (en) | Method for treating and recycling electroplating chromium-containing wastewater through ion exchange | |
| CN104370392A (en) | Treatment method for smelting waste water containing sulfuric acid and heavy metal | |
| CN109811130B (en) | Method for recovering thallium and mercury from smelting acid wastewater | |
| CN107335399B (en) | Method for separating and recovering heavy metal anions and cations in water through phase change regulation | |
| CN102350201B (en) | Ion precipitation separating agent for flue gas desulphurization solution and use method thereof | |
| CN112941330A (en) | Petroleum coke smoke dust treatment method | |
| CN109336232A (en) | A method of nickel-containing waste water is handled using recycling silicon bath soil | |
| CN111250034A (en) | Modification method and application of desulfurization slag | |
| CN110433630B (en) | Deep purification and mercury recovery process for mercury in lead-zinc smelting flue gas |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20240124 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Applicant after: CHINA PETROLEUM & CHEMICAL Corp. Country or region after: China Applicant after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Applicant before: CHINA PETROLEUM & CHEMICAL Corp. Country or region before: China Applicant before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |
|
| TA01 | Transfer of patent application right |