CN111957180A - Process for treating low concentration acid and/or acid radical in gas or solution - Google Patents
Process for treating low concentration acid and/or acid radical in gas or solution Download PDFInfo
- Publication number
- CN111957180A CN111957180A CN202010816471.5A CN202010816471A CN111957180A CN 111957180 A CN111957180 A CN 111957180A CN 202010816471 A CN202010816471 A CN 202010816471A CN 111957180 A CN111957180 A CN 111957180A
- Authority
- CN
- China
- Prior art keywords
- solution
- salt
- acid
- concentration
- low
- 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
- 239000002253 acid Substances 0.000 title claims abstract description 150
- 238000000034 method Methods 0.000 title claims abstract description 70
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 238000004821 distillation Methods 0.000 claims abstract description 6
- 238000005194 fractionation Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 199
- 150000003839 salts Chemical class 0.000 claims description 141
- 239000007864 aqueous solution Substances 0.000 claims description 79
- -1 inorganic acid radical anion Chemical class 0.000 claims description 74
- 150000001450 anions Chemical class 0.000 claims description 73
- 239000011347 resin Substances 0.000 claims description 63
- 229920005989 resin Polymers 0.000 claims description 63
- 150000007522 mineralic acids Chemical class 0.000 claims description 60
- 239000012528 membrane Substances 0.000 claims description 57
- 150000007524 organic acids Chemical class 0.000 claims description 53
- 238000000909 electrodialysis Methods 0.000 claims description 47
- 239000007788 liquid Substances 0.000 claims description 45
- 150000003254 radicals Chemical class 0.000 claims description 40
- 239000000126 substance Substances 0.000 claims description 26
- 230000001172 regenerating effect Effects 0.000 claims description 22
- 238000005868 electrolysis reaction Methods 0.000 claims description 18
- 239000003513 alkali Substances 0.000 claims description 15
- 238000001179 sorption measurement Methods 0.000 claims description 12
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 8
- 239000012670 alkaline solution Substances 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 150000001768 cations Chemical class 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 238000004508 fractional distillation Methods 0.000 claims description 2
- 150000007513 acids Chemical class 0.000 claims 2
- 239000008346 aqueous phase Substances 0.000 claims 2
- 239000012141 concentrate Substances 0.000 abstract description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 100
- 239000007789 gas Substances 0.000 description 86
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 77
- 229960000583 acetic acid Drugs 0.000 description 34
- 229910001415 sodium ion Inorganic materials 0.000 description 29
- 238000002474 experimental method Methods 0.000 description 26
- 235000011121 sodium hydroxide Nutrition 0.000 description 26
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 21
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 17
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 17
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 17
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 15
- 238000010521 absorption reaction Methods 0.000 description 14
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 13
- 238000004448 titration Methods 0.000 description 13
- 238000006243 chemical reaction Methods 0.000 description 12
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 description 11
- 238000007599 discharging Methods 0.000 description 9
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 8
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 8
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000009835 boiling Methods 0.000 description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 6
- 229910052794 bromium Inorganic materials 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- 235000006408 oxalic acid Nutrition 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 230000008929 regeneration Effects 0.000 description 5
- 238000011069 regeneration method Methods 0.000 description 5
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 230000009286 beneficial effect Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 229910017052 cobalt Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 4
- 229910052748 manganese Inorganic materials 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 239000003957 anion exchange resin Substances 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000002485 combustion reaction Methods 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 2
- 229940006460 bromide ion Drugs 0.000 description 2
- 230000005684 electric field Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012362 glacial acetic acid Substances 0.000 description 2
- 239000003014 ion exchange membrane Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003472 neutralizing effect Effects 0.000 description 2
- 239000001632 sodium acetate Substances 0.000 description 2
- 235000017281 sodium acetate Nutrition 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 150000001449 anionic compounds Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000110 cooling liquid Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 229910001412 inorganic anion Inorganic materials 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000001103 potassium chloride Substances 0.000 description 1
- 235000011164 potassium chloride Nutrition 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical group [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/38—Removing components of undefined structure
- B01D53/40—Acidic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/77—Liquid phase processes
- B01D53/78—Liquid phase processes with gas-liquid contact
-
- 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
- C02F1/02—Treatment of water, waste water, or sewage by heating
- C02F1/04—Treatment of water, waste water, or sewage by heating by distillation or evaporation
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
-
- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/469—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis
- C02F1/4693—Treatment of water, waste water, or sewage by electrochemical methods by electrochemical separation, e.g. by electro-osmosis, electrodialysis, electrophoresis electrodialysis
-
- 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
- C02F1/42—Treatment of water, waste water, or sewage by ion-exchange
- C02F2001/422—Treatment of water, waste water, or sewage by ion-exchange using anionic exchangers
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- Analytical Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Hydrology & Water Resources (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention provides a process for treating low-concentration acid and/or acid radical in gas or solution, belonging to the field of process concentration. The invention is applied to concentrate the water-soluble acid and/or acid radical with low concentration in the gas or the solution to high concentration, so that the obtained water-soluble acid with low concentration has no use value, simultaneously, the consumption of a large amount of heat value (steam) in the concentration process by a distillation or fractionation or rectification method is avoided, and the problem that some kinds of water-soluble acid cannot be separated from water to cause concentration when the concentration is lower is further avoided.
Description
Technical Field
The invention belongs to the field of process concentration, and particularly relates to a process for treating low-concentration acid and/or acid radical in gas or solution.
Background
At present, for the low-concentration water-soluble acid and/or acid radical contained in the solution in the industry, because the concentrated water-soluble acid obtained by separating water by using the principle of different boiling points is recycled by using a distillation method or a fractional distillation or rectification method, the consumption of a heat value (generally using steam) used in an evaporation process is large, and the economic value is low; at the same time, the acid and/or acid radical cannot be separated from water by methods having different boiling points at lower concentrations, for example, azeotropes are formed or the acid concentration is very low.
At present, the economic value of acid recovery from acid concentrated to high concentration is extremely difficult for the industry to concentrate water-soluble acid and/or acid radical contained in gas at low concentration. For example, in the oxidation process of the terephthalic acid production device, the oxidation process is mainly to feed p-xylene into an oxidation reactor, the p-xylene reacts with oxygen in the air to produce terephthalic acid, a cobalt, manganese and bromine three-way catalyst (acetic acid is used as a solvent) is required to be added in the reaction process, hydrobromic acid is also added in the reaction process, the concentration of the cobalt, manganese and bromine catalysts in the reaction process is maintained, the oxygen is partially consumed by the oxygen and does not participate in the reaction, so that gas mainly containing nitrogen, acetic acid, hydrobromic acid and the like is generated after the reaction, the acetic acid in the gas is recovered to be tail gas of the oxidation process, the tail gas mainly contains organic matters and hydrobromic acid, the tail gas is finally discharged to the atmosphere after a series of application and treatment, the organic matters in the tail gas are combusted by combustion before being discharged to the atmosphere, but the tail gas after the combustion still contains low-concentration hydrobromic acid (the mass concentration of hydrobromic acid is generally less than 0.1 HBr kg/ton of the ).
Because of the difficulty and the consideration of economic value, most of the low-concentration acid and/or acid radicals contained in the solution are directly discharged or enter sewage treatment under the general current situation, and are not recycled, so that the acid value is wasted, the load of the sewage is increased, and the environmental pollution is caused; finally, in the general state, the low-concentration water-soluble acid and/or acid radical contained in the gas is directly discharged without being recovered, so that the value of the acid is wasted, and the environmental pollution is increased.
Disclosure of Invention
The invention relates to a process for treating low-concentration acid and/or acid radical in gas or solution, which treats the low-concentration water-soluble acid and/or acid radical in the solution (such as aqueous solution) or the low-concentration water-soluble acid and/or acid radical in the gas by the invention to obtain the economic value of concentrated water-soluble acid recovered acid, and simultaneously avoids the social environmental pollution problem caused by direct discharge of the low-concentration water-soluble acid and/or acid radical in the solution (such as aqueous solution) or the low-concentration water-soluble acid and/or acid radical in the gas.
The invention relates to a process for treating low-concentration acid and/or acid radical in gas or solution, which comprises the following steps:
(1) the gas containing a low concentration of acid and/or acid group (such as a concentration of 5% or less), or the solution containing a low concentration of acid and/or acid group (such as an aqueous solution, such as a concentration of 5% or less) is first subjected to a treatment to obtain a solution containing a salt, the treatment specifically including any one of the following:
first, when the gas containing a low concentration of acid and/or acid group is a gas containing a low concentration of inorganic acid and/or inorganic acid group anion, the gas containing a low concentration of inorganic acid and/or inorganic acid group anion is absorbed with water or with a solution (e.g., an aqueous solution) of an alkaline substance to obtain a solution a containing a salt, and the solution a containing a salt is obtained by absorbing and concentrating the low concentration of inorganic acid and/or inorganic acid group anion (a large amount of the low concentration of inorganic acid and/or inorganic acid group anion in the gas is absorbed to a small amount of the high concentration of salt-containing solution a, that is, an absorption liquid); the absorption form can be fixed bed absorption or circulating absorption; the low-concentration inorganic acid and/or inorganic acid radical anions contained in the gas are absorbed into water or alkaline substances, so that the concentration of the inorganic acid and/or inorganic acid radical anions in the discharged gas is reduced, and the environment protection is facilitated;
when the gas containing low-concentration acid and/or acid radical is gas containing low-concentration organic acid and/or organic acid radical anion, the gas containing low-concentration organic acid and/or organic acid radical anion is absorbed by water or by solution (for example, aqueous solution) of alkaline substance to obtain solution b containing salt, and the solution b containing salt is obtained by absorbing and concentrating the low-concentration organic acid and/or organic acid radical anion (the low-concentration organic acid and/or organic acid radical in a large amount of gas is absorbed to become a small amount of high-concentration solution b containing salt, namely absorption liquid); the absorption form can be fixed bed absorption or circulating absorption; absorbing low-concentration organic acid and/or organic acid radical anions contained in the gas into water or alkaline substances, reducing the concentration of the organic acid and/or organic acid radical anions in the discharged gas, and being beneficial to environmental protection;
thirdly, when the gas containing the low-concentration acid and/or acid radical is a gas containing both the low-concentration inorganic acid and/or inorganic acid radical anion and the organic acid and/or organic acid radical anion, the gas containing both the low-concentration inorganic acid and/or inorganic acid radical anion and the organic acid and/or organic acid radical anion is absorbed by water or a solution (for example, an aqueous solution) of an alkaline substance to obtain a solution c containing salt, and the low-concentration inorganic acid and/or inorganic acid radical anion and the organic acid and/or organic acid radical anion are absorbed and concentrated to obtain a solution c containing salt (the low-concentration inorganic acid and/or inorganic acid radical anion and the organic acid and/or organic acid radical anion in a large amount of gas are absorbed into a small amount of high-concentration solution c containing salt, i.e., absorption liquid); the absorption form can be fixed bed absorption or circulating absorption; the low-concentration inorganic acid and/or inorganic acid radical anion and organic acid and/or organic acid radical anion contained in the gas are absorbed into water or alkaline substances, so that the concentration of the inorganic acid and/or inorganic acid radical anion and the concentration of the organic acid and/or organic acid radical anion in the discharged gas are reduced, and the environment protection is facilitated;
when the solution containing the low-concentration acid and/or acid radical is a solution (for example, an aqueous solution) containing a low-concentration inorganic acid, adding an alkaline substance into the solution (for example, the aqueous solution) containing the low-concentration inorganic acid to react to generate a corresponding salt, and concentrating the salt to obtain a solution d containing the salt; concentration can be carried out by means of evaporation;
when the solution containing low-concentration acid and/or acid radical is the solution (for example, aqueous solution) containing low-concentration organic acid, adding alkaline substance into the solution (for example, aqueous solution) containing low-concentration organic acid to react to generate corresponding salt, and concentrating the salt to obtain solution e containing salt; concentration can be carried out by means of evaporation;
when the solution containing low-concentration acid and/or acid radical is a solution (such as an aqueous solution) containing low-concentration inorganic acid and organic acid at the same time, adding an alkaline substance into the solution (such as the aqueous solution) containing low-concentration inorganic acid and organic acid at the same time to react to generate corresponding salt, and concentrating the salt to obtain a solution f containing the salt; concentration can be carried out by means of evaporation;
when the solution containing low-concentration acid and/or acid radical is a solution (such as an aqueous solution) containing low-concentration inorganic acid and/or inorganic acid radical anions, adsorbing the solution (such as the aqueous solution) containing low-concentration inorganic acid and/or inorganic acid radical anions by anion adsorption resin, and then regenerating the anion adsorption resin by using an aqueous solution of an alkaline substance to obtain a regenerated liquid, wherein the regenerated liquid is a solution g containing salt; firstly, adsorbing low-concentration inorganic acid and/or anions in inorganic acid radicals on anion resin through anion resin, and regenerating the anions into regenerated liquid in a salt form through the regeneration of the anion resin, wherein the regenerated liquid obtained in the process is equivalent to a process of concentrating the low-concentration inorganic acid and/or anions in the inorganic acid radicals in the original solution (a large amount of low-concentration inorganic acid and/or inorganic acid radicals in the solution are converted into a small amount of high-concentration solution g containing salt, namely the regenerated liquid);
when the solution containing low-concentration acid and/or acid radical is a solution (such as an aqueous solution) containing low-concentration organic acid and/or organic acid radical anions, adsorbing the solution (such as the aqueous solution) containing low-concentration organic acid and/or organic acid radical anions by anion adsorption resin, and then regenerating the anion adsorption resin by using an aqueous solution of an alkaline substance to obtain a regenerated solution, wherein the regenerated solution is a solution h containing salt; firstly, adsorbing the anions in the low-concentration organic acid and/or organic acid radical on anion resin through the anion resin, and regenerating the anions into a regenerated liquid in a salt form through the regeneration of the anion resin, wherein the regenerated liquid obtained in the process is equivalent to a process for concentrating the low-concentration organic acid and/or organic acid radical anions in the original solution; (a large amount of organic acid and/or organic acid radical with low concentration in the solution is converted into a small amount of solution h with high concentration and containing salt, namely regeneration solution);
ninthly, when the solution containing low concentration of acid and/or acid radical is a solution (such as an aqueous solution) containing low concentration of inorganic acid and/or inorganic acid radical anion and organic acid and/or organic acid radical anion, adsorbing the solution (such as an aqueous solution) containing low concentration of inorganic acid and/or inorganic acid radical anion and organic acid and/or organic acid radical anion by anion adsorption resin, and then regenerating the anion adsorption resin by using an aqueous solution of alkaline substance to obtain a regenerated liquid, wherein the regenerated liquid is a solution i containing salt; firstly, adsorbing low-concentration inorganic acid and/or inorganic acid radical anions and anions in organic acid and/or organic acid radical anions on anion resin through anion resin, and regenerating the anions into regenerated liquid in a salt form through the regeneration of the anion resin, wherein the regenerated liquid obtained in the process is equivalent to a process for concentrating the low-concentration inorganic acid and/or inorganic acid radical anions and the low-concentration organic acid and/or organic acid radical anions in the original solution; (a large amount of low-concentration inorganic acid and/or inorganic acid radical anion, and organic acid and/or organic acid radical anion in the solution are converted into a small amount of high-concentration salt-containing solution i, i.e. regeneration solution);
(2) treating the solution containing the salt in the following way:
subjecting the salt-containing solution a, the salt-containing solution b, the salt-containing solution c, the salt-containing solution d, the salt-containing solution e, the salt-containing solution f, the salt-containing solution g, the salt-containing solution h or the salt-containing solution i to bipolar membrane electrodialysis treatment to obtain an aqueous solution I containing concentrated water-soluble acid and a water-soluble alkali solution I; electrodialysis by a bipolar membrane method: the bipolar membrane is an ion exchange composite membrane, which is usually compounded with a cation exchange layer and an anion exchange layer, under the action of a direct current electric field, the bipolar membrane can dissociate water to form hydrogen ions and hydroxide radicals on two sides of the membrane respectively, the formed hydrogen ions and the formed anions are combined to generate acid for recovery, and the formed hydroxide radicals and cations in salt form alkali which can also be recovered;
or subjecting the salt-containing solution a, the salt-containing solution b, the salt-containing solution c, the salt-containing solution d, the salt-containing solution e, the salt-containing solution f, the salt-containing solution g, the salt-containing solution h or the salt-containing solution i to electrolysis treatment to obtain corresponding electrolysis products, wherein when the salt-containing solution is an aqueous solution of sodium chloride, the electrolysis products are sodium hydroxide, hydrogen gas or chlorine gas.
Based on the technical scheme, preferably,
concentrating the solution a containing the salt to obtain a concentrated solution, and performing bipolar membrane electrodialysis treatment or electrolysis treatment on the concentrated solution;
or the solution b containing the salt is concentrated to obtain a concentrated solution, and the concentrated solution is subjected to bipolar membrane electrodialysis treatment or electrolysis treatment;
or the solution c containing the salt is concentrated to obtain a concentrated solution, and the concentrated solution is subjected to bipolar membrane electrodialysis treatment or electrolysis treatment;
or concentrating the solution g containing the salt to obtain a concentrated solution, and performing bipolar membrane electrodialysis treatment or electrolysis treatment on the concentrated solution;
or concentrating the solution h containing the salt to obtain a concentrated solution, and performing bipolar membrane electrodialysis treatment or electrolysis treatment on the concentrated solution;
or the solution i containing the salt is concentrated to obtain a concentrated solution, and the concentrated solution is subjected to bipolar membrane electrodialysis treatment or electrolysis treatment;
the concentrated solution is obtained in the concentration process, the concentration of salts contained in the concentrated solution is improved, and the operation of the bipolar membrane electrodialysis device or the electrolysis device is facilitated.
Based on the above technical solution, preferably, the solution a containing salt or a concentrated solution thereof, the solution b containing salt or a concentrated solution thereof, the solution c containing salt or a concentrated solution thereof, the solution d containing salt, the solution e containing salt, the solution f containing salt, the solution g containing salt or a concentrated solution thereof, the solution h containing salt or a concentrated solution thereof, or the solution i containing salt or a concentrated solution thereof is cooled before the bipolar membrane electrodialysis treatment or electrolysis, and the bipolar membrane electrodialysis treatment or electrolysis treatment generates heat, and the operation temperature and service life of the membrane in the bipolar membrane electrodialysis device or electrolysis device also require temperature, so the cooling treatment is performed first.
Based on the technical scheme, the alkaline substance is preferably at least one of water-soluble alkaline solution I, hydroxide, carbonate and bicarbonate.
Based on the technical scheme, preferably, the hydroxide, the carbonate and the bicarbonate are at least one of soluble hydroxide, soluble carbonate and soluble bicarbonate, otherwise, insoluble substances are easily formed in the bipolar membrane electrodialysis treatment or the electrolysis treatment process, and the membranes in the bipolar membrane electrodialysis device or the electrolysis device are blocked.
Based on the above technical solution, preferably, the cations in the soluble hydroxides, carbonates and bicarbonates are each independently at least one of potassium and sodium, and the alkaline substances formed by potassium or sodium are generally highly soluble, low in cost and widely available and used in industry.
Based on the technical scheme, preferably, the water solution I containing the concentrated water-soluble acid is directly recovered or separated (heated and separated) by a distillation or fractionation or rectification method by using the principle that the boiling points of the acid and water are different, so as to obtain the re-concentrated water-soluble acid II and a water phase, and the re-concentrated water-soluble acid II is directly recovered; when the acid concentration is low, the method is not suitable for separating water by using methods with different boiling points, but the concentration of the concentrated water-soluble acid obtained by treatment of bipolar membrane electrodialysis or electrolysis and the like is improved, and the improved concentration can reach the concentration which can be separated from water by using methods with different boiling points (for example, compared with the energy consumption of heat values (such as steam), the obtained acid has higher value and the like).
Based on the above technical scheme, preferably, the entrainer is added in the distillation or fractionation or rectification process, and for some kinds of water-soluble acid which can form azeotrope with water by using a method with different boiling points, the entrainer needs to be added (the type and concentration of the entrainer are determined according to the kind, concentration and the like of the water-soluble acid which is separated specifically, and are selected conventionally in the field).
Based on the technical scheme, preferably, the water phase is an aqueous solution containing low-concentration acid and/or acid radical, is directly discharged or is treated according to the process of the invention corresponding to the line of the step (1) to the line of the step (2) again.
The discharge is discharged from the process route of the invention after the treatment of the invention, and the protection of the invention is not affected no matter what specific treatment method (such as discharge to sewage treatment) is adopted after the discharge; the recovery of the invention does not affect the protection of the invention no matter what specific treatment method is adopted after the recovery.
The different steps, units and the like designed by the invention have different and mutually independent purposes, and each step, unit and the like can be independently applied, can be selected and combined in different sequences according to actual requirements, and can only select and apply a part of the steps, units and the like, thereby being within the protection scope of the patent of the invention.
Advantageous effects
The invention relates to a process for treating low-concentration acid and/or acid radical in gas or solution, which is a method for concentrating and recovering the low-concentration acid and/or acid radical which cannot be concentrated in the gas or the solution (such as aqueous solution) to generate economic value, can recover the economic value of the acid, and simultaneously avoids environmental pollution caused by discharging the low-concentration acid and/or acid radical in the gas or the aqueous solution in the prior art.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a diagram of experimental equipment for experiment one and experiment three of example 1;
FIG. 3 is a diagram of experimental facilities for experiment four of example 1.
Detailed Description
Example 1
Experiment one
The experimental set-up was as per fig. 2:
generation of a low concentration hydrogen chloride gas stream: 1L of hydrochloric acid with the mass fraction of 31 percent is put into a conical flask, heated by an alcohol burner, and compressed air is controlled to 300L/min for generating low-concentration hydrogen chloride gas flow, namely simulating 'gas containing low-concentration inorganic acid and/or inorganic acid radical anions';
3L of sodium hydroxide aqueous solution with the mass fraction of 5 percent is placed in the collecting bottle and is used for absorbing and neutralizing hydrogen chloride in the gas, and the aqueous solution in the collecting bottle is analyzed after 4 hours: alkaline, sodium ion 28234ppm, chloride ion 22325ppm (which can be calculated as hydrogen chloride concentration in the gas stream of 0.0009g/L, calculated by assuming that the aqueous solution in the collection bottle is still alkaline, hydrogen chloride in the gas is completely absorbed, 22.325 g/L3L 67g chloride ion is absorbed, gas amount 300L/min 60 min 4 h 72000L, chloride ion concentration in the gas stream 67g/72000L 0.0009g/L), the aqueous solution in the collection bottle is subjected to bipolar membrane electrodialysis, acid compartment effluent: 43171ppm of chloride ion, 18.3ppm of sodium ion and 1.2mol/L of acidity by titration test (in terms of hydrogen ion).
And (4) conclusion: the inorganic acid (such as hydrogen chloride) in the gas is absorbed by the alkaline solution to react to generate salt, the concentration of the inorganic acid in the gas is increased (the inorganic acid with low concentration in a large amount of gas is dissolved and absorbed and accumulated in the alkaline solution to form high-concentration salt), and then the bipolar membrane electrodialysis treatment is carried out to obtain concentrated inorganic acid aqueous solution with relatively high concentration in the acid chamber.
Experiment two
In the oxidation process of the terephthalic acid production device, the oxidation process is mainly to feed paraxylene into air in an oxidation reactor, the paraxylene reacts with oxygen in the air to generate terephthalic acid, a cobalt, manganese and bromine three-way catalyst (acetic acid is used as a solvent) is required to be added in the reaction process, hydrobromic acid is also added in the reaction process, the concentration of the cobalt, manganese and bromine catalysts in the reaction process is maintained, the oxygen is partially consumed by the nitrogen in the reaction process and does not participate in the reaction, so that gas mainly containing nitrogen, acetic acid, hydrobromic acid and the like can be generated after the reaction, the acetic acid in the gas is recovered to be tail gas of the oxidation process, the tail gas mainly contains organic matters and hydrobromic acid, the tail gas is finally discharged to the atmosphere after a series of application and treatment, pollution reduction treatment is required before the tail gas is discharged to the atmosphere, and the general flow is as follows: firstly burning organic matters in the tail gas through combustion, and then absorbing hydrobromic acid (the mass concentration of the hydrobromic acid is generally less than 0.1kg HBr/ton tail gas) in the tail gas by using a sodium hydroxide solution to avoid the pollution of the hydrobromic acid to the atmosphere, wherein the field sampling analysis of an absorption solution of the sodium hydroxide is as follows:
39576ppm of sodium ions and 56143ppm of bromine ions, and the effluent of an acid chamber (the effluent of the acid chamber has slight bubbles during the experiment process and does not influence the operation) is treated by bipolar membrane electrodialysis: 81245ppm of bromide ion, 34.1ppm of sodium ion, and 1.0mol/L of acidity by titration test (in terms of hydrogen ion).
And (4) conclusion: the inorganic acid (such as hydrogen bromide) in the gas is absorbed by the alkaline solution to react to generate salt, the concentration of the inorganic acid in the gas is increased (the inorganic acid with low concentration in a large amount of gas is dissolved and absorbed and accumulated in the alkaline solution to form high-concentration salt), and then the bipolar membrane electrodialysis treatment is carried out to obtain concentrated inorganic acid aqueous solution with relatively high concentration in the acid chamber.
Experiment three
With the experimental equipment of experiment one, 1L of acetic acid was placed in the flask instead, generating a low concentration gaseous acetic acid stream: 1L of glacial acetic acid is put into the conical flask, heated by an alcohol burner, and compressed air is controlled to be 300L/min for generating low-concentration acetic acid gas flow, namely simulating 'gas containing low-concentration organic acid and/or organic acid radical anions';
3L of a 5% sodium hydroxide aqueous solution is placed in the collection bottle for absorbing and neutralizing acetic acid in the gas, and the aqueous solution in the collection bottle is analyzed after 4 hours: alkaline, sodium ions 27965ppm and acetate 32122ppm (calculated as acetic acid concentration in the gas stream of 0.0013g/L, calculated by the following method: since the aqueous solution in the collection bottle is still alkaline, it is inferred that acetic acid in the gas is completely absorbed, 32.122 g/L3L 96g acetic acid is absorbed, gas amount is 300L/min 60 min 4 h 72000L, acetic acid concentration in the gas stream is 96g/72000L 0.0013g/L), the aqueous solution in the collection bottle is subjected to bipolar membrane electrodialysis, and the acid compartment produces water: 58514ppm acetic acid, 15.5ppm sodium ion, 1.0mol/L acidity by titration test (hydrogen ion meter).
And (4) conclusion: absorbing organic acid (such as acetic acid) in gas by using alkaline solution to react to generate salt, wherein the low-concentration organic acid in the gas corresponds to the concentration increasing process (the low-concentration organic acid in a large amount of gas is dissolved and absorbed and accumulated in alkali liquor to form high-concentration salt), and then treating by using bipolar membrane electrodialysis to obtain relatively high-concentration concentrated organic acid aqueous solution in an acid chamber.
Experiment four
The experimental set-up was as per fig. 3:
the formation of a low concentration gaseous "hydrogen chloride + acetic acid" stream:
1L of hydrochloric acid with the mass fraction of 31% is put into the conical flask 1, heated by an alcohol burner, and compressed air is controlled at 300L/min to generate low-concentration hydrogen chloride gas flow;
placing 1L of glacial acetic acid in the conical flask 2, heating by using an alcohol lamp, and controlling 300L/min of compressed air for generating low-concentration acetic acid gas flow;
mixing the gas produced by the conical flasks 1 and 2, namely, introducing a low-concentration gas flow containing low-concentration hydrogen chloride + acetic acid, namely simulating gas containing low-concentration inorganic acid and/or inorganic acid radical anions and organic acid and/or organic acid radical anions into a collecting bottle, placing 3L of sodium hydroxide aqueous solution with the mass fraction of 10% in the collecting bottle for absorbing the hydrogen chloride + acetic acid in the neutralized gas, and analyzing the aqueous solution in the collecting bottle after 4 hours: alkaline, sodium ion 58898ppm, chloride ion 25413ppm (which can be calculated as hydrogen chloride concentration in the gas stream of 0.001g/L, by inference that the aqueous solution in the collection bottle is still alkaline, hydrogen chloride in the gas is completely absorbed, 25.413 g/L3L 76g chloride is absorbed, and gas amount is 300L/min 60 min 4 h 72000L, so chloride ion concentration in the gas stream of 67g/72000L 0.001g/L), acetate 29912ppm (which can be inferred as acetic acid concentration in the gas stream of 0.00125g/L, by inference that the aqueous solution in the collection bottle is still alkaline, acetic acid in the gas stream of 29.912 g/L3L 90g acetic acid is absorbed, 300L/min 60 min 4 h 72000L 7225 g/000L 72000 g acetic acid in the gas stream of 7225 g/min 0.00125 g/000L), and (3) carrying out bipolar membrane electrodialysis treatment on the aqueous solution in the collecting bottle, and discharging water from an acid chamber: 35889ppm of chloride ion, 44423ppm of acetic acid, 31.2ppm of sodium ion, and 1.75mol/L of acidity by titration test (in terms of hydrogen ion).
And (4) conclusion: the mixture of low-concentration inorganic acid (such as hydrogen chloride) + organic acid (such as acetic acid) in the gas is absorbed by alkaline solution to react to generate salt, and the low-concentration inorganic acid and organic acid in the gas correspond to the concentration increasing process (the low-concentration inorganic acid and organic acid in a large amount of gas are dissolved and absorbed and accumulated in alkali liquor to form high-concentration salt), and then the bipolar membrane electrodialysis treatment is carried out to obtain relatively high-concentration concentrated mixed aqueous solution containing the inorganic acid and the organic acid in an acid chamber.
Example 2
Experiment one
Preparing a low-concentration inorganic acid aqueous solution, preparing 100L of a hydrogen chloride aqueous solution with the mass fraction of 1%, adding 1.1KG of sodium hydroxide to perform acid-base neutralization reaction, evaporating and concentrating until the volume of the residual 20L is naturally cooled to the normal temperature, and testing as follows: sodium ion 31122ppm, chloride ion 51495ppm, and acid chamber effluent after bipolar membrane electrodialysis treatment: chloride ion 71334ppm, sodium ion 19.7ppm, acidity by titration test 2mol/L (hydrogen ion meter).
And (4) conclusion: the low-concentration inorganic acid reacts with alkali to generate salt, the salt aqueous solution is beneficial to concentration, and the concentrated inorganic acid aqueous solution with relatively high concentration can be obtained in an acid chamber through bipolar membrane electrodialysis treatment.
Experiment two
Preparing an aqueous solution of low-concentration organic acid, preparing 100L of an aqueous solution of acetic acid with the mass fraction of 1%, adding 0.67KG of sodium hydroxide for acid-base neutralization reaction, evaporating and concentrating until the volume of the residual about 20L, and naturally cooling to normal temperature, wherein the test is as follows: 19334ppm of sodium ions and 50099ppm of acetate, and performing bipolar membrane electrodialysis treatment, wherein the acid chamber effluent: 91573ppm acetic acid, 21.2ppm sodium ion, 1.5mol/L acidity by titration test (hydrogen ion meter).
And (4) conclusion: the low-concentration organic acid reacts with alkali to generate salt, the salt water solution is beneficial to concentration, and the concentrated organic acid water solution with relatively high concentration can be obtained in an acid chamber through bipolar membrane electrodialysis treatment.
Experiment three
Preparing a low-concentration mixed aqueous solution of inorganic acid and organic acid, preparing 100L of a mixed aqueous solution of 0.5% hydrogen chloride and 0.5% acetic acid by mass fraction, adding 0.9KG of sodium hydroxide to perform acid-base neutralization reaction, evaporating and concentrating until the volume of the mixture is about 20L, and naturally cooling to normal temperature, wherein the test is as follows: 25539ppm of sodium ions, 24845ppm of chloride ions and 25153ppm of acetate ions, and the acid chamber effluent is treated by bipolar membrane electrodialysis: 36665ppm of chloride ion, 37123ppm of acetic acid, 15.9ppm of sodium ion, and 1.65mol/L of acidity by titration test (in terms of hydrogen ion).
And (4) conclusion: the low-concentration mixed solution of inorganic acid and organic acid reacts with alkali to generate salt, the aqueous solution of the salt is beneficial to concentration, and the concentrated mixed solution containing the inorganic acid and the organic acid with relatively high concentration can be obtained in an acid chamber through bipolar membrane electrodialysis treatment.
Example 3
Experiment one
20L of a 1% aqueous solution of hydrogen chloride was prepared, 1L of an anion resin (the anion resin was activated with 2L of 5% sodium hydroxide in advance and washed with water) was passed through the resin to adsorb chloride ions, and then the residual liquid in the resin was discharged and regenerated with 2L of a 5% aqueous solution of sodium hydroxide, and the regenerated liquid was analyzed as follows: 27773ppm of sodium ions and 28328ppm of chloride ions, and performing bipolar membrane electrodialysis treatment, wherein the acid chamber effluent: 49965ppm chloride ion, 22.4ppm sodium ion, 1.4mol/L acidity by titration test (hydrogen ion meter).
And (4) conclusion: and (2) adsorbing anions of the inorganic acid by using anion resin, regenerating the anion resin by using alkali liquor to obtain salt corresponding to the inorganic acid radical (and adsorbing and regenerating the anion resin to obtain regenerated liquid, wherein the anion is a concentration process), and performing bipolar membrane electrodialysis treatment on the salt to obtain a concentrated aqueous solution containing the inorganic acid with relatively high concentration in an acid chamber.
Experiment two
Preparing 20L of aqueous HBr solution with the mass fraction of 1%, passing through 1L of anion resin (the anion resin is activated by 2L of sodium hydroxide with the mass fraction of 5% in advance and is used after being washed by water) to adsorb bromide ions, then discharging residual liquid in the resin, and regenerating the residual liquid by 2L of aqueous sodium hydroxide with the mass fraction of 5%, wherein the analysis of the regenerated liquid is as follows: 27773ppm of sodium ions and 55313ppm of bromine ions, and performing bipolar membrane electrodialysis treatment, wherein the acid chamber effluent: 90119ppm of bromide ion, 28.3ppm of sodium ion, and 1.13mol/L of acidity by titration test (in terms of hydrogen ion).
And (4) conclusion: and (2) adsorbing anions of the inorganic acid by using anion resin, regenerating the anion resin by using alkali liquor to obtain salt corresponding to the inorganic acid radical (and adsorbing and regenerating the anion resin to obtain regenerated liquid, wherein the anion is a concentration process), and performing bipolar membrane electrodialysis treatment on the salt to obtain a concentrated aqueous solution containing the inorganic acid with relatively high concentration in an acid chamber.
Experiment three
Preparing 1% oxalic acid aqueous solution 20L, passing through 1L anion resin (anion resin is activated by 2L sodium hydroxide with mass fraction of 5% and used after washing), adsorbing acid radical generated by oxalic acid ionization, discharging residual liquid in the resin, regenerating by 2L sodium hydroxide aqueous solution with mass fraction of 5%, and analyzing the regenerated liquid as follows: 28433ppm of sodium ions, performing bipolar membrane electrodialysis treatment, discharging water from an acid chamber: sodium ion 27.6ppm, 0.25mol/L oxalic acid.
And (4) conclusion: the low-concentration organic acid is adsorbed by anion resin, and then the anion resin is regenerated by alkali liquor, so that salt corresponding to the organic acid radical can be obtained (and the anion resin is adsorbed and regenerated to obtain regenerated liquid, which is a concentration process for anions).
Experiment four
Preparing 20L of mixed aqueous solution of 0.5% hydrogen chloride and 0.5% oxalic acid, adsorbing with 1L of anion resin (the anion resin is activated with 2L of 5% sodium hydroxide and washed with water), discharging residual liquid, regenerating with 2L of 5% sodium hydroxide aqueous solution, and separating the regenerated liquid as follows: 28197ppm of sodium ions and 22517ppm of chloride ions, and the following steps of bipolar membrane electrodialysis treatment, acid chamber effluent: 34314ppm of chloride ion, 14.1ppm of sodium ion, 0.11mol/L of oxalic acid, and 1.15mol/L of acidity (calculated by hydrogen ion) according to titration test.
And (4) conclusion: after the mixed acid of low-concentration inorganic acid and organic acid is adsorbed by anion resin, the anion resin is regenerated by lye, salt corresponding to the mixed acid of the inorganic acid and the organic acid is obtained (and the anion resin is adsorbed and regenerated to obtain regenerated liquid, and anion is a concentration process).
Example 4
Experiment one
Preparing 20L of sodium chloride + 1% potassium chloride aqueous solution with the mass fraction of 1%, adsorbing chloride ions by passing through 1L of anion resin (the anion resin is activated by 2L of sodium hydroxide with the mass fraction of 5% in advance and is used after being washed by water), discharging residual liquid in the resin, and regenerating the residual liquid by using 2L of sodium hydroxide aqueous solution with the mass fraction of 5%, wherein the analysis of the regenerated liquid is as follows: 26983ppm of sodium ions and 29892ppm of chloride ions, and the acid chamber effluent is treated by bipolar membrane electrodialysis: 47816ppm of chloride ion, 22.4ppm of sodium ion and 1.3mol/L of acidity measured by titration (in terms of hydrogen ion).
And (4) conclusion: inorganic anion with low concentration is adsorbed by anion resin, and then the anion resin is regenerated by alkali liquor, so that salt corresponding to inorganic acid radicals can be obtained (and the anion resin is adsorbed and regenerated to obtain regenerated liquid, and the anion is a concentrated concentration process), and the salt is subjected to bipolar membrane electrodialysis treatment to obtain concentrated aqueous solution containing inorganic acid with relatively high concentration in an acid chamber.
Experiment two
20L of sodium acetate aqueous solution with the mass fraction of 0.5% is prepared, 1L of anion resin (the anion resin is activated by 2L of sodium hydroxide with the mass fraction of 5% in advance and is used after being washed by water) is passed to adsorb acetate, then residual liquid in the resin is discharged, the resin is regenerated by 2L of sodium hydroxide aqueous solution with the mass fraction of 5%, and the analysis of the regenerated liquid is as follows: 28433ppm of sodium ions and 13128ppm of acetate, performing bipolar membrane electrodialysis treatment, and discharging water from an acid chamber: sodium ion 27.6ppm, acetic acid 23452ppm, acidity by titration test (hydrogen ion) 0.4 mol/L.
And (4) conclusion: after adsorbing acid radicals of low-concentration organic acid radicals by using anion resin, regenerating the anion resin by using alkali liquor to obtain salts corresponding to the organic acid radicals (and adsorbing and regenerating the anion resin to obtain regenerated liquid, namely a concentration process for anions), and performing bipolar membrane electrodialysis treatment on the salts to obtain a concentrated aqueous solution containing the organic acid with relatively high concentration in an acid chamber.
Experiment three
Preparing 20L of mixed aqueous solution of 0.4% sodium chloride and 0.5% sodium acetate, adsorbing with 1L of anion resin (the anion resin is activated with 2L of 5% sodium hydroxide and washed with water), discharging residual liquid, regenerating with 2L of 5% sodium hydroxide aqueous solution, and separating the regenerated liquid as follows: 27127ppm of sodium ions, 19818ppm of chloride ions and 9893ppm of acetate, and through bipolar membrane electrodialysis treatment, acid chamber effluent: 29370ppm of chloride ion, 16.3ppm of sodium ion, 13452ppm of acetic acid, and 1.05mol/L of acidity by titration test (in terms of hydrogen ion).
And (4) conclusion: the mixed solution of low-concentration inorganic acid radical anion and organic acid radical anion is absorbed by anion resin, the anion resin is regenerated by alkali liquor, the mixture salt corresponding to the inorganic acid radical anion and the organic acid radical anion is obtained (and the anion resin is absorbed and regenerated to obtain regenerated liquid, and the anion is a concentration process), and the salt is subjected to bipolar membrane electrodialysis treatment to obtain a concentrated mixed aqueous solution containing the inorganic acid and the organic acid in an acid chamber.
Description of the drawings:
in the above embodiments 1 to 4, the bipolar membrane electrodialysis is performed by using bipolar membrane electrodialysis experimental equipment provided by the tawnzhou blue-natural environmental technologies corporation, where the bipolar membrane electrodialysis membrane stack of three chambers is used as the equipment, and both the acid chamber and the alkali chamber use demineralized water as the absorption solution, the highest given voltage is set to 35V, the membrane voltage is monitored from the beginning of the experiment, and when the membrane voltage rises to approach the given voltage, the experiment is ended, and the water quality index of the effluent of the acid chamber is tested, and the anion exchange resin is a conventional 201 × 7 type strong basic anion exchange resin, and the experiment selects a 201 × 7 type strong basic anion exchange resin of the eastern great chemical brand.
Example 5
Since this part is common chemical engineering knowledge, the electrolytic sodium chloride aqueous solution (for example, the aqueous solution in the collection bottle of the first experiment in example 1, the cooling liquid of 20L in volume of the first experiment in example 2, the regenerating liquid of the first experiment in example 3, the regenerating liquid of the first experiment in example 4, etc.) does not need to be tested again, and the principle of the chemical reaction is briefly described as follows:
under the action of an electric field, hydroxide ions and chloride ions with negative electricity move to the anode; since the positively charged sodium ions and hydrogen ions move to the cathode, chlorine gas is formed at the anode and hydrogen gas is formed at the cathode.
If the method is carried out in an electrolytic cell of an ion exchange membrane, the obtained products are sodium hydroxide, hydrogen and chlorine (the principle of an ion membrane caustic soda method); if no ion exchange membrane is present, the product is sodium hypochlorite and the like.
The above non-limiting examples enable one of ordinary skill in the art to more fully understand the present invention, but are not intended to limit the invention in any way.
The discharge is discharged from the process route of the invention after the treatment of the invention, and the protection of the invention is not affected no matter what specific treatment method is adopted after the discharge; the recovery of the invention does not affect the protection of the invention no matter what specific treatment method is adopted after the recovery.
The different steps, units and the like designed by the invention have different and mutually independent purposes, and each step, unit and the like can be independently applied, can be selected and combined in different sequences according to actual requirements, and can only select and apply a part of the steps, units and the like, thereby being within the protection scope of the patent of the invention.
Claims (9)
1. A process for treating low concentrations of acids and/or acid radicals in a gas or solution, characterized in that the process is routed:
(1) the method comprises the following steps of firstly treating a gas containing low-concentration acid and/or acid radicals or a solution containing low-concentration acid and/or acid radicals to obtain a solution containing salt, wherein the treatment specifically comprises any one of the following modes:
when the gas containing low-concentration acid and/or acid radical is gas containing low-concentration inorganic acid and/or inorganic acid radical anion, absorbing the gas by using water or solution of alkaline substance to obtain solution a containing salt;
absorbing the gas containing low-concentration acid and/or acid radical by using water or a solution of an alkaline substance to obtain a solution b containing salt when the gas containing low-concentration acid and/or acid radical is the gas containing low-concentration organic acid and/or organic acid radical anions;
thirdly, when the gas containing the low-concentration acid and/or acid radical is gas containing low-concentration inorganic acid and/or inorganic acid radical anions and organic acid and/or organic acid radical anions, absorbing the gas by using water or solution of alkaline substances to obtain solution c containing salt;
when the solution containing the low-concentration acid and/or acid radical is the solution containing the low-concentration inorganic acid, adding an alkaline substance to react to generate corresponding salt, and concentrating the salt to obtain a solution d containing the salt;
when the solution containing low-concentration acid and/or acid radical is the solution containing low-concentration organic acid, adding alkaline substance to react to generate corresponding salt, and then concentrating the salt to obtain a solution e containing salt;
sixthly, when the solution containing the low-concentration acid and/or acid radical is a solution containing both low-concentration inorganic acid and organic acid, adding an alkaline substance to react to generate corresponding salt, and concentrating the salt to obtain a solution f containing the salt;
seventhly, when the solution containing the low-concentration acid and/or acid radical is the solution containing the low-concentration inorganic acid and/or inorganic acid radical anions, adsorbing the solution by anion adsorption resin, and then regenerating the anion adsorption resin by using an aqueous solution of an alkaline substance to obtain a regenerated liquid, wherein the regenerated liquid is a salt-containing solution g;
when the solution containing the low-concentration acid and/or acid radical is a solution containing low-concentration organic acid and/or organic acid radical anions, adsorbing the solution by anion adsorption resin, and then regenerating the anion adsorption resin by using an aqueous solution of an alkaline substance to obtain a regenerated liquid, wherein the regenerated liquid is a solution h containing salt;
ninthly, when the solution containing the low-concentration acid and/or acid radical is a solution containing low-concentration inorganic acid and/or inorganic acid radical anions and organic acid and/or organic acid radical anions, adsorbing by anion adsorption resin, and then regenerating the anion adsorption resin by using an aqueous solution of an alkaline substance to obtain a regenerated liquid, wherein the regenerated liquid is a solution i containing salt;
(2) treating the solution containing the salt in the following way:
subjecting the salt-containing solution a, the salt-containing solution b, the salt-containing solution c, the salt-containing solution d, the salt-containing solution e, the salt-containing solution f, the salt-containing solution g, the salt-containing solution h or the salt-containing solution i to bipolar membrane electrodialysis treatment to obtain an aqueous solution I containing concentrated water-soluble acid and a water-soluble alkali solution I;
or subjecting the solution a containing salt, the solution b containing salt, the solution c containing salt, the solution d containing salt, the solution e containing salt, the solution f containing salt, the solution g containing salt, the solution h containing salt or the solution i containing salt to electrolytic treatment.
2. The process according to claim 1,
the salt-containing solution a, the salt-containing solution b, the salt-containing solution c, the salt-containing solution g, the salt-containing solution h or the salt-containing solution i are concentrated to obtain a concentrated solution, and the concentrated solution is subjected to bipolar membrane electrodialysis treatment or electrolysis treatment.
3. The process according to claim 1 or 2, wherein the salt-containing solution a or a concentrated solution thereof, the salt-containing solution b or a concentrated solution thereof, the salt-containing solution c or a concentrated solution thereof, the salt-containing solution d, the salt-containing solution e, the salt-containing solution f, the salt-containing solution g or a concentrated solution thereof, the salt-containing solution h or a concentrated solution thereof, or the salt-containing solution i or a concentrated solution thereof is cooled before being subjected to the bipolar membrane electrodialysis treatment or electrolysis treatment.
4. The process of claim 1, wherein the alkaline substance is at least one of water-soluble alkaline solution i, hydroxide, carbonate, bicarbonate.
5. The process of claim 4, wherein the hydroxide, carbonate or bicarbonate is at least one of a soluble hydroxide, carbonate or bicarbonate.
6. The process of claim 5, wherein the cations in the soluble hydroxide, carbonate and bicarbonate are each independently at least one of potassium and sodium.
7. The process according to claim 1, wherein the aqueous solution I containing the concentrated water-soluble acid is recovered or the aqueous solution I containing the concentrated water-soluble acid is separated by distillation or fractional distillation or rectification to obtain a re-concentrated aqueous solution II of the water-soluble acid and an aqueous phase; and recovering the re-concentrated water-soluble acid aqueous solution II.
8. The process according to claim 7, wherein an entrainer is added during the distillation or fractionation or rectification.
9. The process according to claim 7 or 8, wherein the aqueous phase is a solution containing a low concentration of acids and/or acid groups, which is discharged directly or treated again according to the route of the process according to claim 1.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010816471.5A CN111957180A (en) | 2020-08-13 | 2020-08-13 | Process for treating low concentration acid and/or acid radical in gas or solution |
| CN202110039367.4A CN112807949A (en) | 2020-08-13 | 2020-08-13 | Process for treating low concentration acid and/or acid radical in solution |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010816471.5A CN111957180A (en) | 2020-08-13 | 2020-08-13 | Process for treating low concentration acid and/or acid radical in gas or solution |
Related Child Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110039367.4A Division CN112807949A (en) | 2020-08-13 | 2020-08-13 | Process for treating low concentration acid and/or acid radical in solution |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111957180A true CN111957180A (en) | 2020-11-20 |
Family
ID=73365572
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110039367.4A Pending CN112807949A (en) | 2020-08-13 | 2020-08-13 | Process for treating low concentration acid and/or acid radical in solution |
| CN202010816471.5A Pending CN111957180A (en) | 2020-08-13 | 2020-08-13 | Process for treating low concentration acid and/or acid radical in gas or solution |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202110039367.4A Pending CN112807949A (en) | 2020-08-13 | 2020-08-13 | Process for treating low concentration acid and/or acid radical in solution |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN112807949A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1449529A (en) * | 1973-11-21 | 1976-09-15 | Tokico Ltd | Process for purifying chromic acid waste water containing chromate ions and recovering a chromic acid solution |
| JP2006131982A (en) * | 2004-11-09 | 2006-05-25 | Jfe Steel Kk | Processing method for pickling waste liquid and processing equipment for pickling waste liquid |
| WO2016193579A1 (en) * | 2015-06-05 | 2016-12-08 | Herakles | Treatment of effluent from hydrolysis of chlorinated gases. |
| CN107960062A (en) * | 2015-06-11 | 2018-04-24 | Bl 科技公司 | bipolar electrodialysis method and system |
| CN108455680A (en) * | 2018-03-30 | 2018-08-28 | 江苏宝钢精密钢丝有限公司 | A kind of iron and steel pickling waste liquid green resourceization utilizes method |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3787304A (en) * | 1972-01-31 | 1974-01-22 | Allied Chem | Production of hf from fluorine by-products |
| US5228962A (en) * | 1991-02-01 | 1993-07-20 | Allied-Signal Inc. | Separation/recovery of ammonium salts via electrodialytic water splitting |
| CA2592926C (en) * | 2007-07-03 | 2015-02-17 | Aristos Energy Inc. | Method for sour gas treatment |
| JP2013244430A (en) * | 2012-05-24 | 2013-12-09 | Swing Corp | Method and apparatus for treating copper chloride-containing acidic waste liquid |
-
2020
- 2020-08-13 CN CN202110039367.4A patent/CN112807949A/en active Pending
- 2020-08-13 CN CN202010816471.5A patent/CN111957180A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1449529A (en) * | 1973-11-21 | 1976-09-15 | Tokico Ltd | Process for purifying chromic acid waste water containing chromate ions and recovering a chromic acid solution |
| JP2006131982A (en) * | 2004-11-09 | 2006-05-25 | Jfe Steel Kk | Processing method for pickling waste liquid and processing equipment for pickling waste liquid |
| WO2016193579A1 (en) * | 2015-06-05 | 2016-12-08 | Herakles | Treatment of effluent from hydrolysis of chlorinated gases. |
| CN107960062A (en) * | 2015-06-11 | 2018-04-24 | Bl 科技公司 | bipolar electrodialysis method and system |
| CN108455680A (en) * | 2018-03-30 | 2018-08-28 | 江苏宝钢精密钢丝有限公司 | A kind of iron and steel pickling waste liquid green resourceization utilizes method |
Non-Patent Citations (5)
| Title |
|---|
| 《发射性理化分析》编写组: "《发射药理化分析 上》", 31 March 1983, 北京：国防工业出版社 * |
| 万端极: "《轻工清洁生产》", 30 September 2006, 北京：中国环境科学出版社 * |
| 恽魁宏: "《有机化学》", 31 March 1982, 人民教育出版社 * |
| 李凯: "《化工行业大气污染控制》", 31 January 2013, 北京：冶金工业出版社 * |
| 解振华: "《中国大百科全书 环境科学》", 31 May 2002, 北京：中国大百科全书出版社 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112807949A (en) | 2021-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP7494216B2 (en) | PFAS Treatment Scheme Using Separation and Electrochemical Rejection | |
| US20210047743A1 (en) | Method for electrochemically reducing carbon dioxide | |
| CN102531927B (en) | Method for preparing tetrapropyl ammonium hydroxide by utilizing bipolar membrane electrodialysis | |
| US6627061B2 (en) | Apparatus and process for electrodialysis of salts | |
| EP2867388B1 (en) | Process and apparatus for generating or recovering hydrochloric acid from metal salt solutions | |
| KR101955889B1 (en) | The removal apparatus of carbon dioxide using concentrated effluent of desalination plant and removing method thereof | |
| CN111268771A (en) | Electrochemical method for dechlorinating and removing heavy metals from incineration fly ash water washing liquid | |
| EP3752660A1 (en) | Integrated electrochemical capture and conversion of carbon dioxide | |
| CN110721563A (en) | Chlorine-containing organic waste gas purification treatment process | |
| CN102229536A (en) | Method for separating amino alkyl alcohol through membrane electrodialysis | |
| CN111957180A (en) | Process for treating low concentration acid and/or acid radical in gas or solution | |
| CN108641023B (en) | Mercury-free polyvinyl chloride production process | |
| CN105060255B (en) | Heavy aromatics recovery and treatment method in oxidized tail gas after hydrogenation liquid oxidation in hydrogen dioxide solution production by anthraquinone process technique | |
| CN101052748A (en) | Synthesis of hydrogen peroxide | |
| EP1480913A1 (en) | Nitrate removal | |
| US20240228419A1 (en) | The production of formic acid or formaldehyde from carbon dioxide | |
| SK286173B6 (en) | Process for improving the purity of quaternary ammonium hydroxides by electrolysis | |
| CN111592167B (en) | Method for treating epoxy resin high-salinity wastewater | |
| CN220194466U (en) | Gas cleaning and recycling system | |
| CN116815209B (en) | Method and device for producing hydrogen by coupling waste water recycling | |
| CN216878626U (en) | Tail gas treatment system | |
| CN220578935U (en) | Device for extracting lithium from raw halogen | |
| US20240240340A1 (en) | Separators for Liquid Products in Oxocarbon Electrolyzers | |
| CN109908979A (en) | A kind of electrically regenerative OH type anion bed failure anion exchange resin method of Bipolar Membrane method | |
| CN118007190A (en) | Recycling device and method for electrolyzed dilute brine |
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 | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20201120 |