CN115990391A - Energy-saving consumption-reducing ammonia recovery method and system - Google Patents
Energy-saving consumption-reducing ammonia recovery method and system Download PDFInfo
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- CN115990391A CN115990391A CN202111214646.6A CN202111214646A CN115990391A CN 115990391 A CN115990391 A CN 115990391A CN 202111214646 A CN202111214646 A CN 202111214646A CN 115990391 A CN115990391 A CN 115990391A
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 226
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 105
- 238000000034 method Methods 0.000 title claims abstract description 42
- 238000011084 recovery Methods 0.000 title claims description 14
- 238000010521 absorption reaction Methods 0.000 claims abstract description 160
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 123
- 239000007788 liquid Substances 0.000 claims abstract description 116
- 239000003054 catalyst Substances 0.000 claims abstract description 86
- 238000009279 wet oxidation reaction Methods 0.000 claims abstract description 72
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims abstract description 39
- 239000007864 aqueous solution Substances 0.000 claims abstract description 24
- 238000004821 distillation Methods 0.000 claims abstract description 15
- 239000007800 oxidant agent Substances 0.000 claims abstract description 12
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 32
- 239000001301 oxygen Substances 0.000 claims description 32
- 229910052760 oxygen Inorganic materials 0.000 claims description 32
- 239000003570 air Substances 0.000 claims description 28
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 26
- 239000007789 gas Substances 0.000 claims description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical group [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 21
- 229910052751 metal Inorganic materials 0.000 claims description 17
- 239000002184 metal Substances 0.000 claims description 17
- 239000000126 substance Substances 0.000 claims description 15
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 13
- 150000007522 mineralic acids Chemical class 0.000 claims description 10
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims description 9
- 239000002105 nanoparticle Substances 0.000 claims description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000002253 acid Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000013078 crystal Substances 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 4
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 2
- 239000011707 mineral Substances 0.000 claims description 2
- 239000000243 solution Substances 0.000 abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 16
- 150000003839 salts Chemical class 0.000 abstract description 10
- 239000002351 wastewater Substances 0.000 abstract description 7
- 238000004064 recycling Methods 0.000 abstract description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 abstract description 5
- -1 amine salt Chemical class 0.000 abstract description 3
- 239000002250 absorbent Substances 0.000 abstract description 2
- 230000002745 absorbent Effects 0.000 abstract description 2
- 239000000203 mixture Substances 0.000 description 24
- 238000002360 preparation method Methods 0.000 description 19
- 238000002156 mixing Methods 0.000 description 11
- 230000003197 catalytic effect Effects 0.000 description 10
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 6
- 239000012670 alkaline solution Substances 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 159000000009 barium salts Chemical class 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000011230 binding agent Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000004134 energy conservation Methods 0.000 description 3
- 238000001704 evaporation Methods 0.000 description 3
- 230000008020 evaporation Effects 0.000 description 3
- 238000010304 firing Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 239000012018 catalyst precursor Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 1
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 description 1
- 239000005695 Ammonium acetate Substances 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229940043376 ammonium acetate Drugs 0.000 description 1
- 235000019257 ammonium acetate Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 235000010948 carboxy methyl cellulose Nutrition 0.000 description 1
- 239000008112 carboxymethyl-cellulose Substances 0.000 description 1
- 239000013064 chemical raw material Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- LAQPNDIUHRHNCV-UHFFFAOYSA-N isophthalonitrile Chemical compound N#CC1=CC=CC(C#N)=C1 LAQPNDIUHRHNCV-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010298 pulverizing process Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
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Abstract
The invention provides a method for recycling ammonia by saving energy and reducing consumption, and belongs to the technical field of ammonia recycling. The method comprises the following steps: contacting the ammonia-containing tail gas with acetic acid absorption liquid in an absorption tower to absorb ammonia in the tail gas to obtain an ammonia-rich absorption liquid and ammonia-free air flow; reacting the ammonium-rich absorption liquid with an oxidant in a wet oxidation reactor with a wet oxidation catalyst bed to obtain an ammonia-containing aqueous solution; and (3) distilling the ammonia-containing water solution in a distillation tower, obtaining crude ammonia gas flow at the top of the tower, and returning tower bottom liquid to the absorption tower. According to the invention, acetic acid is used as an absorbent to form organic amine salt, and a specific high-efficiency catalyst is matched, so that the concentration of acetate in the absorption liquid after wet oxidation is greatly reduced, no salt-containing wastewater is generated, and a large amount of heat is generated in the wet oxidation process.
Description
Technical Field
The invention belongs to the technical field of ammonia recovery, and particularly relates to a method and a system for recovering ammonia by energy conservation and consumption reduction.
Background
Ammonia is a colorless gas at normal temperature and has a strong pungent odor. In the chemical technology related to ammonia, residual ammonia often needs to be separated, if the ammonia is directly discharged, stink is sharp, trees die, the respiratory system and skin of people are damaged, and the local air, environment and production and living modes of residents are influenced. It not only pollutes the atmosphere, but also can eutrophicate the water body after forming rainwater, pollute the water source, cause serious environmental pollution. However, ammonia gas is used as an important chemical raw material, and if recovered, the purpose of saving resources can be achieved. Therefore, the technical level of ammonia-containing tail gas treatment based on environmental protection, energy conservation and consumption reduction is urgently required to be improved.
The most of the excessive ammonia in the existing ammonia oxidation industrial device adopts sulfuric acid to absorb ammonia to form ammonium sulfate, and the process route of crystallizing to obtain the ammonium sulfate, such as an acrylonitrile device, an isophthalonitrile device and the like. In the prior art, a large amount of salt-containing sewage is generated, secondary pollution is caused, and the evaporation concentration energy consumption is high.
Disclosure of Invention
The invention aims to solve the problems of secondary pollution caused by a large amount of salt-containing sewage generated in the prior art and high evaporation concentration energy consumption, and provides a method and a system for recycling ammonia in an energy-saving and consumption-reducing way.
The invention is realized by the following technical scheme:
in a first aspect of the invention, a method for recovering ammonia by energy saving and consumption reduction is provided, which comprises the steps of absorbing ammonia in ammonia-containing tail gas by using acetic acid absorption liquid, then carrying out wet oxidation reaction on the obtained ammonia-rich absorption liquid, and then distilling the obtained ammonia-containing aqueous solution.
The invention is further improved in that:
the method comprises the following specific steps:
s1, contacting ammonia-containing tail gas with acetic acid absorption liquid in an absorption tower to absorb ammonia in the tail gas to obtain an ammonia-rich absorption liquid and ammonia-free air flow;
s2, reacting the ammonium-rich absorption liquid with an oxidant in a wet oxidation reactor with a wet oxidation catalyst bed to obtain an ammonia-containing aqueous solution;
s3, distilling the ammonia-containing aqueous solution in a distillation tower, obtaining crude ammonia gas flow at the top of the tower, and returning tower bottom liquid to the absorption tower.
The invention is further improved in that:
the method further comprises the step of rectifying the crude ammonia gas obtained in the step S3 to obtain an anhydrous ammonia material flow; or adjusting the rectification efficiency to obtain different ammonia content material flows.
The invention is further improved in that:
in step S1, the acetic acid absorption liquid is recycled in the absorption tower, the pH value is 2-6.5, preferably 4-6.5, and/or the concentration of acetic acid in the acetic acid absorption liquid is 3-30%wt, preferably 5-20%wt.
The invention is further improved in that:
in step S1, the acetic acid absorption liquid may further contain an inorganic acid; the concentration of inorganic acid in the acetic acid absorption liquid is 0.1-2.0%wt;
preferably, the inorganic acid is at least one selected from sulfuric acid, nitric acid and hydrochloric acid.
The above-mentioned acetic acid absorbing liquid may be used as a solvent commonly used in the art, and includes an organic solvent and water, preferably water.
The above acetic acid concentration and inorganic acid concentration refer to the mass concentrations of acetic acid, sulfuric acid, nitric acid and hydrochloric acid, respectively.
In general, during the absorption operation, the absorption liquid circulates in the absorption device, and the acid amount of the absorption liquid and the ammonia amount in the tail gas are matched from the neutralization angle.
The invention is further improved in that:
in step S2, the wet oxidation catalyst includes the following components in parts by weight:
(1) 0.1 to 99 parts, preferably 50 to 95 parts, of TiO 2 ；
(2) 0.1 to 99 parts, preferably 5 to 50 parts of BaSO 4 ；
(3) 0.01 to 10 parts, preferably 0.05 to 5 parts, of simple substance of platinum group metal.
The invention is further improved in that:
in the wet oxidation catalyst of step S2:
the platinum group metal simple substance is at least one of Pt, pd, rh and Ru;
and/or, the platinum group metal simple substance is nano particles; preferably, the particle size of the nano particles is less than or equal to 5nm;
and/or, the TiO 2 The crystal form of (a) is anatase.
The invention is further improved in that:
in step S2, the oxidizing agent is an oxygen-containing gas; preferably, the oxygen-containing gas may be pure oxygen, air or oxygen-enriched air having an oxygen content of 35 to 50 v%.
The invention is further improved in that:
in the step S2, the volume ratio of the oxygen in the oxidant to the ammonium-rich absorption liquid is 10-400.
The invention is further improved in that:
in the step S2 of the process,
the temperature of the reaction is 180-300 ℃;
and/or the pressure of the reaction is 3.0-12.0 MPa;
and/or the residence time of the ammonium-rich absorption liquid in the wet oxidation catalyst bed is 10-150 minutes, preferably 10-90 minutes;
the pH value of the ammonia-containing aqueous solution is 7.5-12, preferably 9-11.5.
In a second aspect of the invention, a system for recovering ammonia by energy saving and consumption reduction is provided, which comprises an absorption tower, a wet oxidation reactor and a distillation tower which are sequentially communicated, wherein the distillation tower is communicated with the absorption tower through a pipeline.
Compared with the prior art, the invention has the beneficial effects that:
according to the method for recycling ammonia by energy conservation and consumption reduction, acetic acid is adopted as an absorbent to form organic amine salt, and the organic amine salt is matched with a specific high-efficiency catalyst, so that COD in absorption liquid after wet oxidation is greatly reduced, the salt content in waste water is very low, even no salt-containing waste water is generated, and meanwhile, a large amount of heat is generated in the wet oxidation process.
Drawings
FIG. 1 is a process flow diagram of a process for energy saving, consumption reduction and ammonia recovery of the present invention.
In the figure, 1, an absorption tower, 2, a wet oxidation reactor, 3, a distillation tower, 4, ammonia-containing tail gas, 5, acetic acid, 6, low ammonia gas flow, 7, an ammonium-rich absorption liquid, 8, an oxidant, 9, ammonia-containing aqueous solution, 10, distillation tower bottom liquid, 11 and crude ammonia gas flow are added.
Detailed Description
The invention is described in further detail below with reference to the attached drawing figures:
according to the invention, in the first aspect, the method for recycling ammonia is provided, acetic acid is used as an absorption liquid to absorb ammonia in tail gas, and the obtained ammonia-rich absorption liquid is subjected to wet oxidation reaction and distillation in sequence, so that the purpose of recycling ammonia is achieved.
The method comprises the following steps:
s1, contacting ammonia-containing tail gas with acetic acid absorption liquid in an absorption tower to absorb ammonia in the tail gas to obtain an ammonia-rich absorption liquid and ammonia-free air flow;
s2, reacting the ammonium-rich absorption liquid with an oxidant in a wet oxidation reactor with a wet oxidation catalyst bed to obtain a main ammonia-containing aqueous solution;
s3, distilling the ammonia-containing aqueous solution in a distillation tower, obtaining a crude ammonia gas stream at the tower top, and returning tower bottom liquid to an absorption tower;
in the invention, the method further comprises the step of rectifying the crude ammonia gas obtained in the step S3 to obtain an anhydrous ammonia stream; or adjusting the rectification efficiency to obtain different ammonia content material flows.
In some preferred embodiments of the present invention, in step S1, the acetic acid absorption liquid is recycled in the absorption tower, and the pH value is 2 to 6.5, preferably 4 to 6.5;
and/or the acetic acid concentration is 3 to 30% wt, preferably 5 to 20% wt, wherein the acetic acid absorbing liquid is an aqueous solution of acetic acid.
In step S1, the acetic acid absorption liquid further contains an inorganic acid; the concentration of the inorganic acid in the acetic acid absorption liquid is 0.1 to 2.0 percent by weight;
preferably, the mineral acid selects at least one of sulfuric acid or nitric acid.
In some preferred embodiments of the present invention, in step S2, the wet oxidation catalyst is preferably selected from a heterogeneous wet oxidation catalyst described in chinese patent application CN202010601472.8 filed by the applicant on 28 th 6 th 2020. The present application hereby incorporates in its entirety chinese patent application CN 202010601472.8.
The wet oxidation catalyst comprises the following components in parts by weight:
(1) 0.1 to 99 parts, preferably 50 to 95 parts, of TiO 2 ；
(2) 0.1 to 99 parts, preferably 5 to 50 parts of BaSO 4 ；
(3) 0.01 to 10 parts, preferably 0.05 to 5 parts, of simple substance of platinum group metal; preferably, the platinum group metal element is selected from at least one of Pt, pd, rh, and Ru. The platinum group metal simple substance is nano particles; preferably, the particle size of the nanoparticle is less than or equal to 5nm.
In some embodiments of the invention, the catalyst support is the above-described TiO 2 And BaSO 4 Is a mixture of (a) and (b) the TiO 2 The crystal form of (a) is anatase.
In some embodiments of the invention, the TiO 2 And BaSO 4 The weight ratio is (1-5): 1, and the BaSO 4 The weight ratio of the catalyst to the platinum group metal simple substance is (0.8-8) 0.01; preferably, the TiO 2 And BaSO 4 The weight ratio is (3-4.5): 1, and the BaSO 4 The weight ratio of the catalyst to the platinum group metal simple substance is (0.9-3) 0.01.
TiO in existing catalysts 2 Non-seeding, or partially seeding. Whereas the invention is carried out by introducing BaSO in the catalyst 4 Thereby inhibiting TiO 2 The crystal form of (a) is changed from anatase type with larger specific surface area to rutile type, and TiO is maintained 2 The crystal form is anatase. TiO in catalyst support 2 The crystal form is a pure anatase type, which is more beneficial to improving the dispersity of active components (such as Pt) in the catalyst.
The preparation method of the wet oxidation catalyst comprises the following steps:
(1) Respectively dissolving soluble barium salt and TiOSO 4 Dissolving in water to prepare a solution A and a solution B;
(2) Adding the solution A and the alkaline solution into the solution B, and controlling the pH of the end point to form a precipitate; then the sediment is washed, dried and pulverized to prepare the BaSO-containing liquid 4 And TiO 2 Is a mixture of (a) and (b);
(3) Mixing the mixture with a binder and water, extruding to form strips, drying and roasting to obtain a catalyst carrier;
(4) And loading metal salt containing platinum group metal simple substances on a catalyst carrier, and roasting to obtain the heterogeneous wet oxidation catalyst.
In the present invention, the soluble barium salt may be BaCl 2 、Ba(NO 3 ) 2 Etc. In some embodiments of the invention, the soluble barium salt may be Ba (NO 3 ) 2 。
In some embodiments of the invention, solution A and alkaline solution are slowly added dropwise to solution B with vigorous stirring at a water bath temperature of 20-80 ℃.
In some embodiments of the invention, in step (2), the alkaline solution is selected from at least one of ammonia, urea solution, sodium hydroxide solution, sodium carbonate solution, and sodium bicarbonate solution. In some preferred embodiments of the invention, the alkaline solution is a sodium carbonate solution.
In other embodiments of the present invention, in step (2), the end point pH is controlled to 7 to 11. In some embodiments of the invention, the endpoint pH is controlled to be 7, 8, 9, 10 or 11. In some preferred embodiments of the invention, the endpoint pH is controlled to be 8 to 10. In a still further preferred embodiment of the invention, the end point pH is controlled to 9.
In some embodiments of the invention, in step (3), the binder is selected from at least one of carboxymethyl cellulose (CMC), starch, aluminum sol, silica sol, nitric acid, sulfuric acid, oxalic acid, and citric acid.
In other embodiments of the present invention, in step (3), the firing temperature is 400 to 800 ℃ and the firing time is 1 to 6 hours.
In some embodiments of the invention, in step (4), the firing is performed at a temperature of 200 to 600 ℃ for a time of 1 to 12 hours.
In some embodiments of the invention, in step (4), the metal salt of the simple substance of the platinum group metal is supported on the catalyst support by an impregnation method.
In some more specific embodiments of the present invention, the method for preparing the catalyst specifically comprises the steps of:
1) Respectively adding a certain amount of Ba (NO) 3 ) 2 And TiOSO 4 Dissolving in water to prepare solutions A and B;
2) Slowly dripping the solution A and a certain amount of alkaline solution into the solution B in a water bath at 20-80 ℃ under the condition of intense stirring, and controlling the final pH value to be 7-11 to form a precipitate; washing, drying and pulverizing the precipitate to obtain a solution containing BaSO 4 And TiO 2 Is a mixture of (a) and (b);
3) Mixing the mixture, the binder and water in proportion, extruding to form strips, drying and roasting to obtain the catalyst carrier;
4) The metal salt containing platinum group metal simple substance is loaded on the catalyst carrier by an impregnation method, and the multi-phase wet oxidation catalyst is prepared after roasting.
The method has the characteristics of short preparation flow, high dispersity of the noble metal active components of the prepared wet oxidation catalyst and excellent catalytic oxidation activity.
In the invention, the treatment effect of the catalyst on the ammonium-rich absorption liquid can be evaluated by the following method, and the specific evaluation method is as follows:
90ml of the catalyst was charged into a wet oxidation reactor (the reactor is a fixed bed reactor), and an ammonium-rich absorption liquid after absorbing tail ammonia was used as a raw material, mixed with oxygen, and passed through the wet oxidation reactor with a catalyst bed.
Results: by adopting the technical scheme of the invention, the catalyst can effectively reduce the acetic acid content in the absorption liquid, and after wet oxidation treatment, all acetate radicals in the absorption liquid are removed or the residues are very little, so that the problem of salt-containing wastewater is solved, and a better technical effect is achieved.
It will be appreciated by those skilled in the art that the above methods of evaluating the catalyst only give experimental results on aqueous solutions of ammonium acetate, but those skilled in the art will appreciate that this is for illustration, example, or the same, and is not intended to limit the scope of the organic wastewater being treated, and that the catalysts of the present invention achieve comparable technical results when faced with wastewater containing other specific organic compounds.
In some embodiments of the invention, in step S2, the oxidizing agent is an oxygen-containing gas; the oxygen-containing gas may be pure oxygen, air or oxygen-enriched air with an oxygen content of 35-50 v%.
In other embodiments of the present invention, in step S2, the volume ratio of oxygen in the oxidizing agent to the ammonium-rich absorption liquid is 10 to 400.
In some embodiments of the invention, in step S2, the temperature of the reaction is 180 to 300 ℃ and the pressure of the reaction is 3.0 to 12.0MPa.
In other embodiments of the invention, the residence time of the ammonium enriched absorption liquid in the wet oxidation catalyst bed in step S2 is 10 to 150 minutes, preferably 10 to 90 minutes.
In other embodiments of the invention, in step S2, the aqueous ammonia-containing solution has a pH of 7.5 to 12, preferably 9 to 11.5.
In a second aspect of the invention, a process system for recovering ammonia by energy saving and consumption reduction is provided, as shown in fig. 1, wherein the system comprises an absorption tower 1, a wet oxidation reactor 2 and a distillation tower 3 which are sequentially communicated, and the distillation tower 3 is communicated with the absorption tower 1 through a pipeline.
The specific flow is as follows: contacting the ammonia-containing tail gas 4 with acetic acid absorption liquid in an absorption tower 1 to absorb ammonia in the tail gas to obtain an ammonia-rich absorption liquid 7 and a low ammonia gas stream 6; reacting the ammonium-rich absorption liquid 7 with an oxidant 8 in a wet oxidation reactor 2 with a wet oxidation catalyst bed to obtain an ammonia-containing aqueous solution 9; the ammonia-containing aqueous solution 9 is distilled in the distillation tower 3 to obtain crude ammonia gas flow 11, and tower bottom liquid returns to the absorption tower 1; the crude ammonia stream 11 is rectified to produce an anhydrous ammonia stream or the rectification efficiency is adjusted to produce streams of different ammonia content (not shown).
The innovation point of the invention is as follows: (1) Acetic acid (combination of acetic acid and low concentration inorganic acid: sulfuric acid, nitric acid, etc.) is used as absorption liquid to increase ammonia absorption efficiency, high-efficiency noble metal catalyst is used to remove acetate in the absorption liquid, wet oxidation catalyst is used to treat acetate to directly generate CO 2 The solution is purer ammonia water, which is beneficial to the subsequent treatment and does not generate salt-containing wastewater.
(2) Because the wet oxidation process needs to maintain high temperature, a large amount of heat is generated in the acetate removal process, external heat supplement is not needed in the reaction process, and the method has the energy-saving advantage compared with the crystallization and evaporation of a large amount of heat needed in the ammonium salt production in the prior art.
The embodiments of the present invention all comprise three main steps: preparing a wet oxidation catalyst, and recovering ammonia by catalytic wet oxidation and distilling and rectifying the ammonia. Since the distillation and rectification operation of ammonia belongs to a simple basic chemical unit operation, this will not be described in detail in the examples.
[ example 1 ]
1. Preparation of wet oxidation catalyst
1.1 preparation method of catalyst carrier:
30g of Ba (NO) 3 ) 2 Dissolving in 200mL of water to obtain solution A, mixing 160g of TiOSO 4 Dissolving in 2L water to obtain solution B, and dissolving solution A and 1M sodium carbonate at room temperature and stirring speed of 300 rThe solution was slowly added dropwise to solution B, the final pH of the solution was controlled at 9.0, and stirring was continued for 2h, forming a precipitate. The precipitate was filtered, washed three times with 500mL of deionized water, dried at 80 ℃ for 24 hours after pumping, and the precursor of the catalyst carrier was obtained. 100g of the powdered precursor of the catalyst carrier is uniformly mixed with 5g of CMC, 10g of sulfuric acid and 30g of water, extruded and molded, dried at room temperature for 48h and baked at 550 ℃ for 4h to obtain the catalyst carrier.
1.2 Process for preparing catalysts
0.5gH 2 PtCl 6 Dissolving in 30g of water, immersing 100g of catalyst carrier in the solution at room temperature for 24 hours, and drying at 60 ℃ for 48 hours to obtain the catalyst precursor. The catalyst precursor is calcined for 4 hours at 400 ℃ in an air atmosphere, and the catalyst is a multi-phase wet oxidation catalyst, namely a catalyst C-01. The catalyst comprises Pt in parts by weight 0.19 [BaSO 4 ] 25.02 [TiO 2 ] 74.8 . From a TEM electron micrograph, 30 Pt nanoparticles were taken, and the average particle diameter of the Pt nanoparticles was calculated to be 2.6nm.
The wet oxidation catalyst C-01 above and its preparation are from example 3 of the patent application with application number CN 202010601472.8.
2. Recovery of ammonia using wet oxidation catalyst
Air mixture with ammonia content of 5% by volume is prepared, the air mixture is bubbled through an absorption bottle (simulated absorption tower) filled with 1000ml of absorption liquid at a speed of 100ml/min, the acetic acid content in the absorption liquid is 8% wt, the sulfuric acid content is 2.0% wt, the pH of the absorption liquid is 5.0, and the absorption liquid rich in ammonium is obtained after absorption. Mixing the high COD ammonium-rich absorption liquid with oxygen, and carrying out catalytic wet oxidation under the conditions of a reaction temperature of 270 ℃ and a pressure of 9MPa by a fixed bed reactor filled with 90mL of catalyst C-01 to obtain an ammonia-containing aqueous solution. The flow rate of the ammonium-rich absorption liquid is 1.5mL/min, and the flow rate of the oxygen is 180mL/min. The reaction results are shown in Table 1.
[ example 2 ]
1. Preparation of wet oxidation catalyst
Catalyst preparation the same as in example 1
2. Recovery of ammonia using wet oxidation catalyst
Air mixture with ammonia content of 5% is prepared, the air mixture is bubbled through an absorption bottle (simulated absorption tower) filled with 1000ml of absorption liquid at a speed of 100ml/min, the acetic acid content in the absorption liquid is 5% wt, the nitric acid content is 0.2% wt, the pH of the absorption liquid is 5.0, and the absorption liquid rich in ammonium is obtained after absorption. Mixing the high COD ammonium-rich absorption liquid with oxygen, and carrying out catalytic wet oxidation under the conditions of a reaction temperature of 270 ℃ and a pressure of 9MPa by a fixed bed reactor filled with 90mL of catalyst C-01 to obtain an ammonia-containing aqueous solution. The flow rate of the ammonium-rich absorption liquid is 2.0mL/min, and the flow rate of oxygen is 150mL/min. The reaction results are shown in tables 1 and 2.
[ example 3 ]
1. Preparation of wet oxidation catalyst
Catalyst preparation the same as in example 1
2. Recovery of ammonia using wet oxidation catalyst
Air mixture with ammonia content of 5% is prepared, the air mixture is bubbled through an absorption bottle (simulated absorption tower) filled with 1000ml of absorption liquid at a speed of 100ml/min, the acetic acid content in the absorption liquid is 15% wt, the pH of the absorption liquid is 5.0, and the absorption liquid rich in ammonium is obtained after absorption. Mixing the high COD ammonium-rich absorption liquid with oxygen, and carrying out catalytic wet oxidation under the conditions of the reaction temperature of 280 ℃ and the pressure of 11MPa by a fixed bed reactor filled with 90mL of catalyst C-01 to obtain an ammonia-containing aqueous solution. The flow rate of the ammonium-rich absorption liquid is 1.5mL/min, and the flow rate of the oxygen is 360mL/min. The reaction results are shown in tables 1 and 2.
[ example 4 ]
1. Preparation of wet oxidation catalyst
Catalyst preparation the same as in example 1
2. Recovery of ammonia using wet oxidation catalyst
Air mixture with ammonia content of 5% by volume is prepared, the air mixture is bubbled through an absorption bottle (simulated absorption tower) filled with 1000ml of absorption liquid at a speed of 100ml/min, the acetic acid content in the absorption liquid is 20% wt, the nitric acid content is 0.5% wt, the pH of the absorption liquid is 6.5, and the absorption liquid rich in ammonium is obtained after absorption. Mixing the high COD ammonium-rich absorption liquid with oxygen, and carrying out catalytic wet oxidation under the conditions of the reaction temperature of 290 ℃ and the pressure of 11MPa by a fixed bed reactor filled with 90mL of catalyst C-01 to obtain an ammonia-containing aqueous solution. The flow rate of the ammonium-rich absorption liquid is 1.0mL/min, and the flow rate of oxygen is 290mL/min. The reaction results are shown in tables 1 and 2.
[ example 5 ]
1. Preparation of wet oxidation catalyst
Catalyst preparation the same as in example 1
2. Recovery of ammonia using wet oxidation catalyst
Air mixture with ammonia content of 5% by volume is prepared, and the mixture is bubbled through an absorption bottle (simulated absorption tower) filled with 1000ml of absorption liquid at a speed of 100ml/min, wherein acetic acid content in the absorption liquid is 3% wt, pH of the absorption liquid is 4.0, and the absorption liquid rich in ammonium is obtained after absorption. Mixing the high COD ammonium-rich absorption liquid with oxygen, and carrying out catalytic wet oxidation under the conditions of the reaction temperature of 180 ℃ and the pressure of 3MPa by a fixed bed reactor filled with 90mL of catalyst C-01 to obtain an ammonia-containing aqueous solution. The flow rate of the ammonium-rich absorption liquid is 2.0mL/min, and the flow rate of the oxygen is 90mL/min. The reaction results are shown in tables 1 and 2.
[ example 6 ]
1. Preparation of wet oxidation catalyst
Catalyst preparation the same as in example 1
2. Recovery of ammonia using wet oxidation catalyst
Air mixture with ammonia content of 5% by volume is prepared, and the mixture is bubbled through an absorption bottle (simulated absorption tower) filled with 1000ml of absorption liquid at a speed of 100ml/min, wherein the acetic acid content in the absorption liquid is 10% wt, the pH of the absorption liquid is 4.5, and the absorption liquid rich in ammonium is obtained after absorption. Mixing the high COD ammonium-rich absorption liquid with oxygen, and carrying out catalytic wet oxidation under the conditions of the reaction temperature of 250 ℃ and the pressure of 9MPa by a fixed bed reactor filled with 90mL of catalyst C-01 to obtain an ammonia-containing aqueous solution. The flow rate of the ammonium-rich absorption liquid is 1.5mL/min, and the flow rate of oxygen is 220mL/min. The reaction results are shown in tables 1 and 2.
[ example 7 ]
1. Preparation of wet oxidation catalyst
Catalyst preparation the same as in example 1
2. Recovery of ammonia using wet oxidation catalyst
Air mixture with ammonia content of 5% by volume is prepared, the air mixture is bubbled through an absorption bottle (simulated absorption tower) filled with 1000ml of absorption liquid at a speed of 100ml/min, the acetic acid content in the absorption liquid is 12% wt, the sulfuric acid content is 0.1% wt, the pH of the absorption liquid is 5.0, and the absorption liquid rich in ammonium is obtained after absorption. Mixing the high COD ammonium-rich absorption liquid with oxygen, and carrying out catalytic wet oxidation under the conditions of a reaction temperature of 270 ℃ and a pressure of 10MPa by a fixed bed reactor filled with 90mL of catalyst C-01 to obtain an ammonia-containing aqueous solution. The flow rate of the ammonium-rich absorption liquid is 1.5mL/min, and the flow rate of oxygen is 250mL/min. The reaction results are shown in tables 1 and 2.
[ example 8 ]
1. Preparation of wet oxidation catalyst
Catalyst preparation the same as in example 1
2. Recovery of ammonia using wet oxidation catalyst
Air mixture with ammonia content of 5% by volume is prepared, the air mixture is bubbled through an absorption bottle (simulated absorption tower) filled with 1000ml of absorption liquid at a speed of 100ml/min, the acetic acid content of the absorption liquid is 30% wt, the sulfuric acid content of the absorption liquid is 0.2% wt, the pH of the absorption liquid is 5.5, and the absorption liquid rich in ammonium is obtained after absorption. Mixing the high COD ammonium-rich absorption liquid with oxygen, and carrying out catalytic wet oxidation under the conditions of the reaction temperature of 300 ℃ and the pressure of 12MPa by a fixed bed reactor filled with 90mL of catalyst C-01 to obtain an ammonia-containing aqueous solution. The flow rate of the ammonium-rich absorption liquid is 1.0mL/min, and the flow rate of the oxygen is 400mL/min. The reaction results are shown in tables 1 and 2.
The inorganic acid concentrations of the absorption solutions in comparative examples 1, 2 and 3 were prepared to be equivalent to the amounts of the acids in examples 1, 2 and 3.
Comparative example 1
An air mixture with an ammonia content of 5% by volume was prepared and bubbled through an absorption bottle containing 1000ml of absorption liquid at a rate of 100ml/min, the sulfuric acid content of the absorption liquid being 8.5% wt (corresponding to the amount of acid in example 1), and the pH of the absorption liquid after absorption being 5.0. The wet oxidation conditions were the same as in example 1. The reaction results are shown in tables 1 and 2.
Comparative example 2
An air mixture having an ammonia content of 5% by volume was prepared and bubbled through an absorption bottle containing 1000ml of an absorption liquid having a nitric acid content of 5.25% by weight (corresponding to the amount of acid in example 2) at a rate of 100ml/min, and the pH of the absorption liquid after absorption was 5.0. The wet oxidation conditions were the same as in example 2. The reaction results are shown in tables 1 and 2.
[ comparative example 3 ]
An air mixture with an ammonia content of 5% by volume was prepared and bubbled through an absorption bottle containing 1000ml of absorption liquid at a rate of 100ml/min, the sulfuric acid content of the absorption liquid being 12.25% wt (corresponding to the acid content in example 3), and the pH of the absorption liquid after absorption being 5.0. The wet oxidation conditions were the same as in example 3. The reaction results are shown in tables 1 and 2.
TABLE 1
The wet oxidation reaction time was calculated from the ammonium rich absorption liquid flow rate and the catalyst volume and is not shown in the table.
The flow rate of the ammonia-containing tail gas is not an important attention index, is a fixed value in the experiment and is not listed in the table.
TABLE 2
The ammonium salt concentrations in table 2 include acetate concentrations.
Finally, it should be noted that the above-mentioned technical solution is only one embodiment of the present invention, and various modifications and variations can be easily made by those skilled in the art based on the application methods and principles disclosed in the present invention, and are not limited to the methods described in the above-mentioned specific embodiments of the present invention, therefore, the foregoing description is only preferred, and not meant to be limiting.
Claims (11)
1. A method for recovering ammonia by energy saving and consumption reduction comprises the steps of absorbing ammonia in ammonia-containing tail gas by using acetic acid absorption liquid, carrying out wet oxidation reaction on the obtained ammonia-rich absorption liquid, and then distilling the obtained ammonia-containing aqueous solution.
2. The method according to claim 1, characterized in that it comprises the following specific steps:
s1, contacting ammonia-containing tail gas with acetic acid absorption liquid in an absorption tower to absorb ammonia in the tail gas to obtain an ammonia-rich absorption liquid and ammonia-free air flow;
s2, reacting the ammonium-rich absorption liquid with an oxidant in a wet oxidation reactor with a wet oxidation catalyst bed to obtain an ammonia-containing aqueous solution;
s3, distilling the ammonia-containing aqueous solution in a distillation tower, obtaining crude ammonia gas flow at the top of the tower, and returning tower bottom liquid to the absorption tower.
3. The method according to claim 1 or 2, further comprising rectifying the crude ammonia stream obtained in step S3 to obtain an anhydrous ammonia stream; or adjusting the rectification efficiency to obtain different ammonia content material flows.
4. The method according to claim 2, wherein in step S1, the acetic acid absorption liquid is recycled in the absorption tower, and the pH value is 2 to 6.5, preferably 4 to 6.5;
and/or the acetic acid concentration in the acetic acid absorbing liquid is 3 to 30% wt, preferably 5 to 20% wt.
5. The method according to claim 4, wherein in step S1, the acetic acid absorption liquid further contains a mineral acid; the concentration of inorganic acid in the acetic acid absorption liquid is 0.1-2.0%wt;
preferably, the inorganic acid is at least one selected from sulfuric acid, nitric acid and hydrochloric acid.
6. The method according to claim 2, wherein in step S2, the wet oxidation catalyst comprises the following components in parts by weight:
(1) 0.1 to 99 parts, preferably 50 to 95 parts, of TiO 2 ；
(2) 0.1 to 99 parts, preferably 5 to 50 parts of BaSO 4 ；
(3) 0.01 to 10 parts, preferably 0.05 to 5 parts, of simple substance of platinum group metal.
7. The method according to claim 6, wherein in the wet oxidation catalyst of step S2:
the platinum group metal simple substance is at least one of Pt, pd, rh and Ru;
and/or, the platinum group metal simple substance is nano particles; preferably, the particle size of the nano particles is less than or equal to 5nm;
and/or, the TiO 2 The crystal form of (a) is anatase.
8. The method according to claim 2, wherein in step S2, the oxidizing agent is an oxygen-containing gas; preferably, the oxygen-containing gas may be pure oxygen, air or oxygen-enriched air having an oxygen content of 35 to 50 v%.
9. The method according to claim 2, wherein in step S2, the volume ratio of oxygen in the oxidizing agent to the ammonium-rich absorption liquid is 10 to 400.
10. The method according to claim 2, wherein in step S2,
the temperature of the reaction is 180-300 ℃;
and/or the pressure of the reaction is 3.0-12.0 MPa;
and/or the residence time of the ammonium-rich absorption liquid in the wet oxidation catalyst bed is 10-150 minutes, preferably 10-90 minutes;
the pH value of the ammonia-containing aqueous solution is 7.5-12, preferably 9-11.5.
11. An energy-saving and consumption-reducing ammonia recovery system according to the method for energy-saving and consumption-reducing ammonia recovery according to any one of claims 1 to 10, characterized in that the system comprises an absorption tower, a wet oxidation reactor and a distillation tower which are communicated in sequence, and the distillation tower bottom is communicated with the absorption tower through a pipeline.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0364310A1 (en) * | 1988-05-26 | 1990-04-18 | Elf Atochem S.A. | Method of catalytically purifying an aqueous effluent containing acetic acid |
| JPH1110173A (en) * | 1997-06-19 | 1999-01-19 | Teijin Ltd | Method for recovering acetic acid from waste water containing acetic acid |
| JPH11147093A (en) * | 1997-11-18 | 1999-06-02 | Teijin Ltd | Control method of catalytic wet oxidizing treatment apparatus |
| CN106964247A (en) * | 2017-04-24 | 2017-07-21 | 中国石油化工股份有限公司 | Handling process containing ammonia flow in acrylonitrile installation |
| CN107866222A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | Without thiamine process method in acrylonitrile reactor device |
| CN213193164U (en) * | 2020-06-22 | 2021-05-14 | 天津精华石化有限公司 | Acid volatile liquid storage and leakage prevention integrated machine |
-
2021
- 2021-10-19 CN CN202111214646.6A patent/CN115990391A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0364310A1 (en) * | 1988-05-26 | 1990-04-18 | Elf Atochem S.A. | Method of catalytically purifying an aqueous effluent containing acetic acid |
| JPH1110173A (en) * | 1997-06-19 | 1999-01-19 | Teijin Ltd | Method for recovering acetic acid from waste water containing acetic acid |
| JPH11147093A (en) * | 1997-11-18 | 1999-06-02 | Teijin Ltd | Control method of catalytic wet oxidizing treatment apparatus |
| CN107866222A (en) * | 2016-09-26 | 2018-04-03 | 中国石油化工股份有限公司 | Without thiamine process method in acrylonitrile reactor device |
| CN106964247A (en) * | 2017-04-24 | 2017-07-21 | 中国石油化工股份有限公司 | Handling process containing ammonia flow in acrylonitrile installation |
| CN213193164U (en) * | 2020-06-22 | 2021-05-14 | 天津精华石化有限公司 | Acid volatile liquid storage and leakage prevention integrated machine |
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