CN112980498A - Method and device for efficiently oxidizing sweetening alkali liquor and recovering disulfide - Google Patents
Method and device for efficiently oxidizing sweetening alkali liquor and recovering disulfide Download PDFInfo
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- CN112980498A CN112980498A CN202110152302.0A CN202110152302A CN112980498A CN 112980498 A CN112980498 A CN 112980498A CN 202110152302 A CN202110152302 A CN 202110152302A CN 112980498 A CN112980498 A CN 112980498A
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- 239000003513 alkali Substances 0.000 title claims abstract description 359
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 title claims abstract description 197
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000001590 oxidative effect Effects 0.000 title claims abstract description 21
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 162
- 230000003647 oxidation Effects 0.000 claims abstract description 160
- 238000011069 regeneration method Methods 0.000 claims abstract description 88
- 239000007789 gas Substances 0.000 claims abstract description 87
- 230000008929 regeneration Effects 0.000 claims abstract description 87
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 54
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 19
- 238000011084 recovery Methods 0.000 claims abstract description 17
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 82
- 238000000926 separation method Methods 0.000 claims description 60
- 239000007788 liquid Substances 0.000 claims description 48
- 239000000945 filler Substances 0.000 claims description 40
- 238000012856 packing Methods 0.000 claims description 23
- 238000006477 desulfuration reaction Methods 0.000 claims description 18
- 230000023556 desulfurization Effects 0.000 claims description 18
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 claims description 17
- 239000003054 catalyst Substances 0.000 claims description 17
- 239000000835 fiber Substances 0.000 claims description 17
- 229910001220 stainless steel Inorganic materials 0.000 claims description 15
- 239000010935 stainless steel Substances 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 13
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- 239000001301 oxygen Substances 0.000 claims description 13
- 230000014759 maintenance of location Effects 0.000 claims description 10
- 210000003632 microfilament Anatomy 0.000 claims description 7
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 6
- 150000002019 disulfides Chemical class 0.000 claims description 6
- 229920002313 fluoropolymer Polymers 0.000 claims description 6
- 239000004811 fluoropolymer Substances 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 229920006295 polythiol Polymers 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- 238000009736 wetting Methods 0.000 claims description 6
- 238000010008 shearing Methods 0.000 claims description 4
- 239000000853 adhesive Substances 0.000 claims description 3
- 230000001070 adhesive effect Effects 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 3
- SXFQDYORBVIULR-UHFFFAOYSA-N azane;cobalt(2+) Chemical compound N.[Co+2] SXFQDYORBVIULR-UHFFFAOYSA-N 0.000 claims description 3
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical group [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 claims description 3
- 239000002352 surface water Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 230000000630 rising effect Effects 0.000 claims description 2
- CSABAZBYIWDIDE-UHFFFAOYSA-N sulfino hydrogen sulfite Chemical compound OS(=O)OS(O)=O CSABAZBYIWDIDE-UHFFFAOYSA-N 0.000 claims 11
- 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 1
- 238000005516 engineering process Methods 0.000 abstract description 13
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229930195733 hydrocarbon Natural products 0.000 description 29
- 150000002430 hydrocarbons Chemical class 0.000 description 29
- 239000004215 Carbon black (E152) Substances 0.000 description 25
- 229910052717 sulfur Inorganic materials 0.000 description 18
- 239000011593 sulfur Substances 0.000 description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 17
- 239000002904 solvent Substances 0.000 description 17
- 238000000605 extraction Methods 0.000 description 12
- 230000002441 reversible effect Effects 0.000 description 8
- 239000012670 alkaline solution Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 239000003518 caustics Substances 0.000 description 3
- 238000004581 coalescence Methods 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 125000002228 disulfide group Chemical group 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- -1 sodium thiolate Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 230000004931 aggregating effect Effects 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 238000000409 membrane extraction Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
- C10G19/08—Recovery of used refining agents
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Treating Waste Gases (AREA)
Abstract
The invention discloses a method and a device for efficiently oxidizing sweetening alkali liquor and recovering disulfide, wherein the device comprises an alkali liquor oxidation tower, the bottom of the alkali liquor oxidation tower is connected with a sweetening alcohol alkali liquor line, the top of the alkali liquor oxidation tower is connected with a tail gas line, one side of the alkali liquor oxidation tower is connected with the upper part of an alkali liquor regeneration tower through an oxidized alkali liquor line, the bottom of the alkali liquor regeneration tower is connected with a regenerated alkali liquor line, and the top of the alkali liquor regeneration tower is connected with the tail gas line. According to the method and the device for efficiently oxidizing the desulfurized alcohol alkali liquor and recovering the disulfide, the air catalytic oxidation technology of the packed tower is adopted, the sodium mercaptan oxidation efficiency can reach more than 95%, the recovery rate of the disulfide can reach 85-95%, the alkali liquor after the disulfide is separated is subjected to air stripping and nitrogen two-stage air stripping of the packed tower to remove the residual disulfide, the content of the disulfide in the regenerated alkali liquor can be removed to be below 10 mu g/g, and the content of the sodium mercaptan is below 100 mu g/g.
Description
Technical Field
The invention relates to the technical field of liquid hydrocarbon sweetening, in particular to a method and a device for efficiently oxidizing sweetening alkali liquor and recovering disulfide.
Background
Liquefied gas produced by an oil refinery comprises catalytic liquefied gas, coking liquefied gas, saturated liquefied gas and light hydrocarbon recovery liquefied gas, the liquefied gas contains four carbon components produced by a gas separation device, and also contains five carbon components, gasoline or naphtha and liquid hydrocarbons such as condensate oil produced by an oil-gas field, and basically contains dozens to thousands of microgram g/g of mercaptan, and the liquid hydrocarbons are generally required to be subjected to mercaptan removal refining treatment according to the requirement of a downstream process on the total sulfur of the liquid hydrocarbons.
The most common and most economical method for removing mercaptan from liquid hydrocarbon at present is sodium hydroxide alkali liquor extraction, mercaptan in liquid hydrocarbon reacts with sodium hydroxide to generate sodium mercaptide, alkali liquor after extraction is oxidized by air catalysis, the sodium mercaptide reacts with oxygen to generate sodium hydroxide and disulfide, and the alkali liquor is regenerated, but the generated disulfide is required to be removed as low as possible, so that the phenomenon that the total sulfur of the liquid hydrocarbon is increased due to the fact that the disulfide in regenerated alkali liquor is back-extracted into the liquid hydrocarbon is avoided or reduced.
The MEROX technology developed by American Ring-and-ball oil products company (UOP) in 1958 is a liquid hydrocarbon sweetening and alkali liquor oxidation regeneration technology with earlier industrial application, sweetening alkali liquor is subjected to large-air-volume air catalytic oxidation in a filler oxidation tower and then is sent to a disulfide separation tank for sedimentation separation, as the temperature of the alkali liquor oxidation process is high (generally in the range of 55-65 ℃) and disturbance is severe, disulfide generated by oxidation is seriously emulsified with the alkali liquor, so that the disulfide is difficult to be separated into layers in the disulfide separation tank, the content of the disulfide in the alkali liquor of a system is rapidly increased, the total sulfur of the product liquid hydrocarbon is rapidly increased, and the total sulfur of the product liquid hydrocarbon can be controlled only by frequently replacing the alkali liquor. The lower the requirement on the total sulfur content of the liquefied gas product is, the more the alkali liquor is replaced, the larger the discharge amount of the alkali residues is, and the total sulfur of the liquefied gas product is periodically fluctuated along with the replacement of the alkali liquor.
Chinese patent CN101705108A (named as a liquid hydrocarbon sweetening technology capable of deeply removing total sulfur, application number 200910250279.8) and Chinese patent CN104711023A (named as a liquefied gas sweetening tail gas and caustic sludge treatment method and special equipment thereof, application number 201510106262.0) are two related patent technologies, and in the traditional liquid hydrocarbon extraction, oxidation and sweetening process, processes of carrying out three-phase mixing and strengthening regeneration of sweetening alkali liquor, air and solvent oil on the sweetening alkali liquor, carrying out secondary reverse extraction on the oxidized alkali liquor and the solvent oil, separating a regenerated catalyst from an extracting agent and the like are adopted to reduce or avoid the regenerated alkali liquor from aggregating disulfides, solve the problem of high total sulfur of the product liquid hydrocarbon and greatly reduce the discharge amount of caustic sludge. However, the patent technology has the following problems: (1) the hydrocarbon content of the tail gas is about 5-10% due to the volatilization of the solvent oil along with the tail gas in the oxidation tower, so that explosive gas is easily formed, a certain flow of dry gas or nitrogen gas needs to be supplemented in the tail gas, and the solvent oil is seriously damaged, so that the desulfurization cost of the liquid hydrocarbon is increased; (2) the sulfur-containing solvent needs to be subjected to hydrodesulfurization refining, so that the solvent hydrogenation cost is high, and the liquid hydrocarbon desulfurization cost is indirectly increased; (3) part of the solvent oil contains sulfur and phenol, alkali liquor is consumed in the reverse extraction process, and the discharge amount of alkali residues is increased; (4) after the reverse extraction, the solvent oil carries alkali liquor, a washing and dewatering facility needs to be additionally arranged, the process flow of an alkali liquor regeneration unit is increased, and the total investment of a liquid hydrocarbon mercaptan removal device is obviously increased.
Chinese patent CN101371967B (entitled liquefied gas sweetening alkali liquor oxidation regeneration method, application number 200710071004.9), chinese patent CN101469276B (entitled oil-containing alkali liquor separation device and method, application number 200710308071.8), chinese patent CN202446974U (entitled liquefied gas sweetening combined system, application number 201220012653.8), chinese patent CN102757809B (entitled a device and method for gasoline light fraction sweetening and alkali liquor regeneration, application number 201210276509. X), chinese patent CN105038850B (entitled a device and method for condensate sweetening and alkali liquor regeneration recovery disulfide, application number 201510520290.7), chinese patent CN105112092B (entitled condensate liquid membrane fiber sweetening and alkali liquor regeneration solvent reverse extraction device and method, application number 201510521920.2) are six related patent technologies, a part or all of liquid hydrocarbon sweetening alkali liquor enters an oxidation tower for oxidation, the oxidation tower is of an empty tower structure, the alkali liquor enters from the bottom of the tower, the air or the rich oxygen enters from the bottom of the tower and is dispersed into tiny bubbles through a micropore gas distributor to enter the alkali liquor in the tower, the alkali liquor is fully contacted with the microbubbles, and the oxidation temperature of the alkali liquor is in the range of 25-45 ℃ so as to improve the contact area of the alkali liquor and the air and reduce the emulsification of the alkali liquor and the disulfide; forming alkali liquor liquid film extraction emulsified disulfide and standing layering by hydrophilic coalescence packing in a separation zone or a separation tower after oxidation, and recovering about 60 percent of disulfide; and removing residual disulfide from the alkali liquor after partial disulfide separation through air or nitrogen gas stripping, or removing residual disulfide through reverse extraction of solvent oil by a liquid membrane contactor, so that the desulfurized alcohol alkali liquor is regenerated. However, the series of patent technologies have the following problems: (1) the oxidation temperature of the alkali liquor is in the range of 25-45 ℃, which is not the optimal temperature (50-65 ℃) of an alkali liquor oxidation catalyst, an alkali liquor oxidation tower is not filled with a filler, only tiny bubbles are formed by a distributor to improve the gas-liquid contact area, the gas-liquid contact and oxygen diffusion efficiency is low, so that the alkali liquor oxidation rate is low, the alkali liquor oxidation time (3-5 times of the retention time of a filler oxidation tower) can be prolonged only by a desulfurization alcohol alkali liquor partial oxidation mode or a large-volume oxidation tower is designed to ensure that the sufficient alkali liquor oxidation rate is reached, the partial alkali liquor oxidation regeneration mode is not suitable for the sweetening process of high-sulfur liquefied gas, and the large-volume oxidation tower increases the equipment investment; (2) the aperture of the alkali liquor oxidation tower is micron-sized by adopting a gas distributor, the industrial device is easy to block, and the gas distributor is washed by desalted water or swept by steam after being blocked, so that the alkali liquor of the system can be diluted, the discharge amount of alkali residues is greatly increased, and the labor intensity of a post is greatly increased; (3) if the alkali liquor oxidation tower adopts oxygen-enriched air for oxidation, the tail gas has over-high oxygen content and contains disulfide and hydrocarbons, so that potential safety hazards exist; (4) the separation recovery rate of the disulfide is only about 60 percent, the residual disulfide still needs to be removed by adopting reverse extraction solvent oil, the problems that the sulfur-containing solvent oil is hydrogenated to increase the desulfurization cost of liquid hydrocarbon, the discharge amount of alkaline residue is increased by sulfur and phenol in the solvent oil, the sulfur-containing solvent needs to be washed by water and a dehydration facility to increase the investment of a liquid hydrocarbon sweetening device and the like exist, or the residual disulfide needs to be removed by air stripping with larger air volume, and the discharge amount of sulfur-containing tail gas is large.
Chinese patent CN104263403B (named as a method and a device for deeply oxidizing and separating disulfide by sweetening alkali liquor, application number 201410454906.0) and Chinese patent CN204058377U (named as an oil sweetening and alkali liquor oxidation regeneration device, application number 201420514825.0) are related patents, hydrophilic filler is arranged above a liquid distributor of an alkali liquor oxidation tower, lipophilic filler is arranged below an air distributor, the temperature of alkali liquor oxidation reaction is 40-50 ℃, sweetening alkali liquor is sprayed from top to bottom by the liquid distributor, oxidation air forms micro bubbles through the air distributor to reversely contact from bottom to top and complete oxidation reaction, tail gas and generated disulfide float to the upper layer of the alkali liquor and are settled and layered by the hydrophilic coalescent filler, the alkali liquor is sent out of the oxidation tower from the bottom, and is extracted by a fiber membrane extraction contactor and solvent oil to remove residual disulfide, so that the sweetening alkali liquor is regenerated, the hydrophilic filler is a stainless steel wire or a regular filler or a plastic filler which is subjected to surface hydrophilic modification, and the lipophilic filler is lipophilic plastic, resin or stainless steel metal coated with a lipophilic film on the surface. According to the technology, the recovery rate of the disulfide is about 50%, about 10% of the disulfide is taken away with tail gas, the rest 40% of the disulfide is removed through reverse extraction solvent oil, and the problems that the liquid hydrocarbon desulfurization cost is increased, the caustic sludge discharge amount is increased and the device investment is increased due to the hydrogenation of the reverse extraction solvent oil exist.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a method and a device for efficiently oxidizing sweetening alkali liquor and recovering disulfide, which can overcome the defects in the prior art.
In order to achieve the technical purpose, the technical scheme of the invention is realized as follows:
a device for efficiently oxidizing sweetening alkali liquor and recovering disulfide comprises an alkali liquor oxidation tower, wherein the bottom of the alkali liquor oxidation tower is connected with a desulfurization alcohol alkali liquor line, the top of the alkali liquor oxidation tower is connected with a tail gas line, one side of the alkali liquor oxidation tower is connected with the upper part of an alkali liquor regeneration tower through an oxidized alkali liquor line, the bottom of the alkali liquor regeneration tower is connected with a regenerated alkali liquor line, and the top of the alkali liquor regeneration tower is connected with the tail gas line;
the alkali liquor oxidation tower is divided into an upper section and a lower section, the upper section is a separation section, the lower section is an oxidation section, a tail gas desulfurization disulfide coalescer is installed at the top of the separation section, a disulfide separation tank is arranged below the tail gas desulfurization disulfide coalescer, the inner tower wall of the disulfide separation tank is connected with a disulfide line, a disulfide dealkalization coalescer is arranged below the disulfide separation tank, a baffle is arranged below the disulfide dealkalization coalescer, the inner tower wall of the baffle is connected with the oxidized alkali liquor line, a disulfide dealkalization coalescer is arranged in the disulfide separation tank, and an alkali liquor desulfurization disulfide coalescer is arranged in the baffle; an alkali liquor oxidation tower filler is arranged in the oxidation section, an alkali liquor oxidation tower air distributor is arranged below the alkali liquor oxidation tower filler, and the alkali liquor oxidation tower air distributor is connected with an oxidation air line;
a first alkali liquor regeneration tower filler is arranged below an alkali liquor inlet at the upper part of the alkali liquor regeneration tower, a second alkali liquor regeneration tower filler is arranged below the first alkali liquor regeneration tower filler, the second alkali liquor regeneration tower filler is arranged below the second alkali liquor regeneration tower filler, and the second alkali liquor regeneration tower filler is connected with an air stripping nitrogen line;
the mercaptan removal alkali liquor line is provided with a catalyst injector, the oxidation alkali liquor line is provided with an alkali liquor heater, and the regeneration alkali liquor line is provided with an alkali liquor cooler.
Preferably, the filter screens in the tail gas desulfurization coalescer and the alkali liquor desulfurization coalescer are both oleophilic materials, and the pore diameters of the filter screens in the tail gas desulfurization coalescer and the alkali liquor desulfurization coalescer are both 5-15 μm.
Preferably, the filter screens in the tail gas desulfurization coalescer and the alkali liquor desulfurization coalescer adopt blend modified fiber filaments of polythioether and fluoropolymer or stainless steel fiber filaments (stainless steel microfilaments) with the surfaces coated with blend coatings of polythioether and fluoropolymer, the longitudinal and transverse fiber filaments are welded by hot melting without adhesives, and the wetting angle of oil on the surfaces of the fiber filaments is not more than 3 degrees.
Preferably, the filter screens in the first disulfide dealkalizing coalescer and the second disulfide dealkalizing coalescer are both stainless steel microfilaments with surfaces modified by hydrophile, the wetting angle of the surface water of the stainless steel microfilaments is not more than 3 degrees, and the pore diameters of the filter screens in the first disulfide dealkalizing coalescer and the second disulfide dealkalizing coalescer are both 5-15 mu m.
Preferably, 4-8 evenly distributed alkaline solution holes are formed in the bottom of the disulfide separation tank, the aperture of each alkaline solution hole is 2-5mm, and the alkaline solution oxidation tower packing, the alkaline solution regeneration tower packing I and the alkaline solution regeneration tower packing II are all stainless steel regular packing or random packing.
Preferably, the diameter of the separation section is 1.2-1.5 times of that of the oxidation section, the ratio of the inner diameter of the disulfide separation tank to the diameter of the oxidation section and the ratio of the inner diameter of the baffle to the diameter of the oxidation section are not less than 0.8, the ratio of the height of the separation section to the height of the oxidation section is 0.3-0.6, the height-diameter ratio of the oxidation section is 4-8, and the height-diameter ratio of the alkali liquor regeneration tower is 6-10.
According to another aspect of the present invention, there is provided a method for oxidizing a desulfurized alcohol lye and recovering disulfides using the above apparatus, comprising the steps of:
s1, the mercaptan removal alkali liquor with the temperature of 30-45 ℃ enters an alkali liquor oxidation tower from the bottom of the tower, the operation pressure at the top of the alkali liquor oxidation tower is 0.2-0.5MPa, and an alkali liquor oxidation catalyst is continuously or discontinuously added into the alkali liquor through a catalyst injector, so that the catalyst concentration in the alkali liquor is 200 mu g/g;
s2 compressed air is uniformly distributed on the cross section in the tower through an air distributor of the alkali liquor oxidation tower, alkali liquor and air bubbles are sheared and fully contacted by a filler of the alkali liquor oxidation tower in the ascending process of the alkali liquor oxidation tower, sodium mercaptan in the alkali liquor is oxidized into sodium hydroxide and disulfide, the disulfide carries the alkali liquor to continuously float up along with the air bubbles, the alkali liquor carrying the disulfide settles on the lower layer, the boundary position of the disulfide and the alkali liquor is controlled between the top of a baffle and the two bottoms of a disulfide dealkalization coalescer, when the alkali liquor overflows the baffle and passes through the alkali liquor dealkalization coalescer, the emulsified disulfide tiny liquid drops are aggregated into large disulfide liquid drops and float up to a disulfide layer, and the alkali liquor after the disulfide is coalesced and separated sinks under pressure and is conveyed through an alkali liquor oxidation line;
s3, when the disulfide carrying the alkali liquor floats upwards along with the bubbles and passes through the disulfide dealkalizing coalescer II, the emulsified alkali liquor tiny droplets are agglomerated into large alkali liquor droplets and sink to an alkali liquor layer, the disulfide continuously floats upwards with the tail gas and is separated in a tail gas section, and the liquid level of the disulfide is controlled above a disulfide separation groove; when the disulfide enters the disulfide separation tank, micro-emulsified alkali liquor micro-droplets contact the disulfide dealkalization coalescer to coalesce into large alkali liquor droplets and sink to the bottom of the disulfide separation tank, and the large alkali liquor droplets continue to sink to an alkali liquor layer through an alkali liquor hole at the bottom of the disulfide separation tank; when the tail gas passes through a tail gas disulfide removal coalescer at the top of the alkali liquor oxidation tower, small disulfide droplets in the tail gas are gathered into large droplets and dropped to a disulfide layer; the disulfide is discharged through a disulfide line connected in the disulfide separation tank; the tail gas for separating the disulfide is discharged through a tail gas line at the top of the alkali liquor oxidation tower;
s4 heating the alkali liquor from the alkali liquor oxidation tower to 50-65 ℃ by an alkali liquor heater, feeding the heated alkali liquor into an alkali liquor regeneration tower from the upper side, sequentially carrying out air stripping twice by two sections of fillers and air and nitrogen from top to bottom, uniformly distributing compressed air and nitrogen on the cross section in the tower through an air distributor and a nitrogen distributor in the alkali liquor regeneration tower, enabling the alkali liquor and bubbles to reversely flow in the alkali liquor regeneration tower, shearing and fully contacting the fillers in the tower, and dissolving disulfide remaining in the alkali liquor in the bubbles and taking away the disulfide along with tail gas; stripping the bottom layer nitrogen gas and simultaneously removing dissolved oxygen in the alkali liquor; discharging the tail gas containing disulfide from the top of the alkali liquor regeneration tower; the regenerated alkali liquor is discharged from a regenerated alkali liquor line at the bottom of the alkali liquor regeneration tower.
Preferably, the alkali oxidation catalyst is sulfonated cobalt phthalocyanine or ammonium cobalt phthalocyanine sulfonate.
Preferably, the alkali liquor retention time of the packing section of the alkali liquor oxidation tower in the step S1 is 1-4 hours, the operation temperature of the alkali liquor oxidation tower is controlled at 30-45 ℃, and the air flow in the step S2 is 1.5-2.5 times of the air flow required by the theoretical calculation of all oxidation of sodium mercaptide in the sweetening alkali liquor.
Preferably, in the step S4, the retention time of the single-section packing alkali liquor of the alkali liquor regeneration tower is 0.2-0.6 h, the operation temperature of the alkali liquor regeneration tower is controlled at 50-65 ℃, the gas-liquid ratio of stripping air is 10-30:1, and the gas-liquid ratio of stripping nitrogen is 5-10: 1.
The invention has the beneficial effects that: the method and the device for efficiently oxidizing the desulfurized alcohol alkali liquor and recovering the disulfide adopt a packed tower air catalytic oxidation technology, the alkali liquor oxidation retention time is only 1/3-1/2 of the volume of an oxidation tower of an empty tower micro-bubble technology, the sodium mercaptan oxidation efficiency can reach more than 95%, the alkali liquor after oxidation is subjected to multiple coalescence and separation by a hydrophilic filter screen coalescer and a lipophilic filter screen coalescer, the disulfide recovery rate can reach 85-95%, the alkali liquor after disulfide separation is subjected to air stripping and nitrogen two-stage air stripping by a packed tower to remove the residual disulfide, the disulfide content in the regenerated alkali liquor can be removed to be below 10 mu g/g, and the sodium mercaptan content is below 100 mu g/g, meanwhile, the dissolved oxygen in the alkali liquor can be reduced to below 1mg/L by nitrogen gas stripping, so that the problem that the mercaptan cannot be removed because the mercaptan is directly oxidized into disulfide when the regenerated alkali liquor containing the dissolved oxygen is recycled for removing the mercaptan from the liquid hydrocarbon is solved.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings without creative efforts.
FIG. 1 is a schematic diagram of an apparatus for efficiently oxidizing and recovering disulfides in a desulfurized alcohol lye according to an embodiment of the present invention;
FIG. 2 is a schematic structural view of a tail gas desulfurization coalescer according to an embodiment of the invention;
fig. 3 is a schematic structural view of a first disulfide dealkalizing coalescer according to an embodiment of the invention;
fig. 4 is a schematic structural view of a disulfide separation tank according to an embodiment of the present invention;
fig. 5 is a schematic structural view of a second disulfide dealkalized coalescer according to an embodiment of the invention;
FIG. 6 is a schematic structural diagram of a coalescer for removing disulfide from a lye according to an embodiment of the present invention;
FIG. 7 is a schematic structural diagram of a baffle according to an embodiment of the invention;
fig. 8 is a schematic structural diagram of a distributor according to an embodiment of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments that can be derived by one of ordinary skill in the art from the embodiments given herein are intended to be within the scope of the present invention.
Example 1
As shown in fig. 1-8, the apparatus for efficiently oxidizing and recovering disulfide from desulfurized alcohol lye according to the embodiment of the present invention comprises a lye oxidation tower 1, wherein the bottom of the lye oxidation tower 1 is connected with a desulfurized alcohol lye line 21, the top of the lye oxidation tower 1 is connected with a tail gas line 23, one side of the lye oxidation tower 1 is connected with the upper part of a lye regeneration tower 12 through an oxidized lye line 25, the bottom of the lye regeneration tower 12 is connected with a regenerated lye line 28, and the top of the lye regeneration tower 12 is connected with the tail gas line 23; the alkali liquor oxidation tower 1 is divided into an upper section and a lower section, the upper section is a separation section, the lower section is an oxidation section, a tail gas disulfidizing coalescer 2 is installed at the top of the separation section, a disulfidizing separation tank 4 is arranged below the tail gas disulfidizing coalescer 2, the inner tower wall of the disulfidizing separation tank 4 is connected with a disulfidizing line 24, a disulfidizing coalescer II 5 is arranged below the disulfidizing separation tank 4, a baffle 7 is arranged below the disulfidizing coalescer II 5, the inner tower wall of the baffle 7 is connected with an alkali liquor oxidation line 25, a disulfidizing coalescer 3 is arranged in the disulfidizing separation tank 4, and an alkali liquor disulfidizing coalescer 6 is arranged in the baffle 7; an alkali liquor oxidation tower filler 8 is installed in the oxidation section, an alkali liquor oxidation tower air distributor 9 is arranged below the alkali liquor oxidation tower filler 8, and the alkali liquor oxidation tower air distributor 9 is connected with an oxidation air line 22; a first alkali liquor regeneration tower filler 13 is arranged below an alkali liquor inlet at the upper part of the alkali liquor regeneration tower 12, a second alkali liquor regeneration tower filler 15 is arranged below the first alkali liquor regeneration tower filler 13, the second alkali liquor regeneration tower filler 14 is connected with an air stripping air line 26, a second alkali liquor regeneration tower filler 16 is arranged below the second alkali liquor regeneration tower filler 15, and the second alkali liquor regeneration tower nitrogen distributor 16 is connected with an air stripping nitrogen line 27; the desulfurization alcohol alkali liquor line 21 is provided with a catalyst injector 10, the oxidation alkali liquor line 25 is provided with an alkali liquor heater 11, and the regeneration alkali liquor line 28 is provided with an alkali liquor cooler 17.
The filter screens in the tail gas disulfide removal coalescer 2 and the alkali liquor disulfide removal coalescer 6 adopt blend modified fiber filaments of polythioether and fluoropolymer or stainless steel fiber filaments with the surface sprayed with a blend coating of polythioether and fluoropolymer, the longitudinal and transverse fiber filaments are welded by hot melting without adhesives, and the wetting angle of surface oil of the fiber filaments is not more than 3 degrees. The pore diameters of the filter screens in the tail gas disulfide removal coalescer 2 and the alkali liquor disulfide removal coalescer 6 are both 5-15 mu m. The filter screens in the first disulfide dealkalizing coalescer 3 and the second disulfide dealkalizing coalescer 5 are both stainless steel microfilaments with surfaces modified by hydrophile, the wetting angle of the surface water of the stainless steel microfilaments is not more than 3 degrees, and the pore diameters of the filter screens in the first disulfide dealkalizing coalescer 3 and the second disulfide dealkalizing coalescer 5 are both 5-15 mu m. The bottom of the disulfide separation tank 4 is provided with 4-8 evenly distributed alkaline liquid holes, the aperture of the alkaline liquid holes is 2-5mm, and the alkaline liquid oxidation tower packing 8, the alkaline liquid regeneration tower packing I13 and the alkaline liquid regeneration tower packing II 15 are all stainless steel regular packing or random packing. The diameter of the separation section is 1.2-1.5 times of that of the oxidation section, the ratio of the inner diameter of the disulfide separation tank 4 to the diameter of the oxidation section and the ratio of the inner diameter of the baffle 7 to the diameter of the oxidation section are not less than 0.8, the ratio of the height of the separation section to the height of the oxidation section is 0.3-0.6, the height-diameter ratio of the oxidation section is 4-8, and the height-diameter ratio of the alkali liquor regeneration tower 12 is 6-10.
Example 2
The method for oxidizing the desulfurized alcohol lye and recovering the disulfide by using the device of the embodiment 1 comprises the following steps:
s1 mercaptan removal alkali liquor with the temperature of 30-45 ℃ from a liquid hydrocarbon mercaptan removal device enters an alkali liquor oxidation tower 1 from the bottom of the tower, the operating pressure at the top of the alkali liquor oxidation tower 1 is 0.2-0.5MPa, an alkali liquor oxidation catalyst is continuously or discontinuously added into the alkali liquor through a catalyst injector 10 in small flow, the concentration of the catalyst in the alkali liquor is 200 mu g/g, and the alkali liquor oxidation catalyst is sulfonated cobalt phthalocyanine or ammonium cobalt phthalocyanine sulfonate;
s2, uniformly distributing compressed air with a set flow rate on the cross section of the alkali liquor oxidation tower 1 through the alkali liquor oxidation tower air distributor 9 at the bottom of the alkali liquor oxidation tower, shearing and fully contacting alkali liquor and air bubbles by the alkali liquor oxidation tower packing 8 in the process of slowly rising in the alkali liquor oxidation tower 1, and oxidizing sodium mercaptan in the alkali liquor into sodium hydroxide and disulfide; the density of the disulfide is lower than that of the alkali liquor, a small amount of alkali liquor carried with the disulfide continuously floats upwards along with the bubbles, and the alkali liquor carried with the small amount of disulfide is settled on the lower layer; the interface positions of the disulfide and the alkali liquor are controlled between the top of the baffle 7 and the bottom of the disulfide dealkalization coalescer II 5, when the alkali liquor after separating the tail gas and the disulfide overflows the baffle 7 and passes through the alkali liquor dealkalization coalescer 6, the emulsified tiny droplets of the disulfide are coalesced into large droplets of the disulfide and float to a disulfide layer when contacting with oleophilic fiber filaments of the coalescer, and the alkali liquor after coalescing and separating the disulfide sinks and is sent to an alkali liquor regeneration tower 12 through the line pressure of the alkali liquor; the control of the oxidation temperature and the oxidation air flow of the alkali liquor is a necessary measure for reducing the disturbance of the alkali liquor and the disulfide so as to realize the separation and recovery of the disulfide; after the disulfide is coalesced and separated, 500-1000 mu g/g of disulfide can be dissolved in the alkali liquor, and the content of sodium mercaptide in the alkali liquor is not more than 100 mu g/g;
s3, when the disulfide with a small amount of alkali liquor continuously floats upwards through the disulfide dealkalization coalescer II 5 along with air bubbles, the emulsified alkali liquor tiny droplets are coalesced into large alkali liquor droplets when contacting hydrophilic fiber filaments of the coalescer and sink to an alkali liquor layer; the disulfide and the tail gas continuously float upwards and are separated in a tail gas section, and the liquid level of the disulfide is controlled above the disulfide separation tank 4; when the disulfide enters the disulfide separation tank 4, micro-emulsified alkali liquor micro-droplets are coalesced into large alkali liquor droplets when contacting hydrophilic fiber filaments of the disulfide dealkalizing coalescer I3 and sink to the bottom of the disulfide separation tank 4, and the large alkali liquor droplets continue to sink to an alkali liquor layer through an alkali liquor hole at the bottom of the disulfide separation tank 4; when the tail gas passes through a tail gas disulfide removal coalescer 2 at the top of the alkali liquor oxidation tower 1, small disulfide droplets in the tail gas are gathered into large droplets and drop to a disulfide layer; the disulfide is discharged out of the apparatus through a disulfide line 24 connected in the disulfide separation tank 4; the tail gas for separating the disulfide is discharged out of the device through a tail gas line 23 at the top of the alkali liquor oxidation tower 1; 300-500 mu g/g alkali liquor is dissolved in the discharged disulfide, and no free disulfide is entrained in tail gas; the recovery rate of the disulfide can reach 85 to 95 percent;
s4 heating the alkali liquor from the alkali liquor oxidation tower 1 to 50-65 ℃ by the alkali liquor heater 11, feeding the heated alkali liquor into the alkali liquor regeneration tower 12 from the upper side, sequentially carrying out air stripping twice by two sections of fillers and air and nitrogen from top to bottom, uniformly distributing the compressed air and nitrogen on the cross section in the alkali liquor regeneration tower 12 through an air distributor and a nitrogen distributor in the alkali liquor regeneration tower, enabling the alkali liquor and bubbles to reversely flow in the alkali liquor regeneration tower 12 and further shearing and fully contacting the fillers in the regeneration tower, and dissolving the residual disulfide in the alkali liquor in the bubbles and taking away the disulfide along with tail gas; the bottom layer nitrogen gas is stripped, and simultaneously the dissolved oxygen in the alkali liquor can be removed; the disulfide-containing tail gas is discharged out of the device from the top of the tower; the regenerated alkali liquor is discharged from a regenerated alkali liquor line 28 at the bottom of the alkali liquor regeneration tower 12, is cooled to about 40 ℃ by an alkali liquor cooler 17, and is sent to liquid hydrocarbon for cyclic mercaptan removal; the content of sodium mercaptide in the regenerated alkali liquor is not more than 100 mu g/g, the content of disulfide is not more than 10 mu g/g, and the content of dissolved oxygen is not more than 1 mg/L.
The distributor in the steps S2 and S4 is a multi-row distribution pipe with holes punched at the top of the tube array, the hole diameter of the holes punched at the top of the tube array is 1-3mm, the hole distance is 20-50mm, the outlet air speed is controlled at 20-40m/S, and if the air quantity is too large and the number of the air outlets is too large, holes can be uniformly punched at two sides of the distribution pipe at the same time.
In the step S1, the retention time of the alkali liquor in the packing section of the alkali liquor oxidation tower 1 is 1-4 hours, the retention time is selected to be large for the alkali liquor with high sodium thiolate content, the operation temperature of the alkali liquor oxidation tower 1 is controlled at 30-45 ℃, the air flow in the step S2 is 1.5-2.5 times of the air flow required by the theoretical calculation of all oxidation of the sodium thiolate in the sweetening alkali liquor, namely, the air flow surplus rate is controlled within the range of 50-150%.
In the step S4, the retention time of the single-section packing alkali liquor of the alkali liquor regeneration tower 12 is 0.2-0.6 h, the operation temperature of the alkali liquor regeneration tower 12 is controlled at 50-65 ℃, the gas-liquid ratio of stripping air is 10-30:1, the gas-liquid ratio of stripping nitrogen is 5-10:1, or the stripping can be designed to be completely carried out by the nitrogen, and if the total gas amount is not changed, the stripping air distributor is cancelled.
Experimental example 1:
a50 ten thousand ton/year catalytic liquefied gas sweetening device of a certain petrochemical company has the sweetening alkali liquor flow rate of 12t/h and the sodium mercaptan content of 600-plus 1000 mug/g, and adopts the method described in the embodiment 2 to carry out oxidation regeneration, wherein the operation temperature of an alkali liquor oxidation tower is 30-40 ℃, the pressure is 0.2-0.3MPa, the operation temperature of an alkali liquor regeneration tower is 50-55 ℃, the pressure is about 0.1MPa, the sodium mercaptan content of regenerated alkali liquor is 30-50 mug/g, the disulfide content is 5-9 mug/g, and the total sulfur of refined liquefied gas is less than 5mg/Nm3The disulfide recovery is about 95 tons per year and about 85%.
Experimental example 2:
a 4 ten thousand tons/year coking liquefied gas sweetening device of a certain petrochemical company, the flow rate of the sweetening alkaline liquor is 1.5t/h, the content of sodium mercaptan is 6000-Oxidizing regeneration, wherein the operating temperature of an alkali liquor oxidation tower is 40-45 ℃, the pressure is 0.3-0.4MPa, the operating temperature of the alkali liquor regeneration tower is 60-65 ℃, the pressure is 0.15MPa, the content of sodium mercaptide in the regenerated alkali liquor is 70-90 mu g/g, the content of disulfide is 5-10 mu g/g, and the total sulfur of the refined liquefied gas is 30-80mg/Nm3The disulfide recovery is about 116 tons per year and about 95%.
Experimental example 3:
a 10 ten thousand ton/young hydrocarbon recovery liquefied gas sweetening device of a certain petrochemical company, the flow rate of sweetening alkali liquor is 3t/h, the sodium mercaptan content is 500 plus 800 mug/g, the method of the embodiment 2 is adopted for oxidation regeneration, the operation temperature of an alkali liquor oxidation tower is 40-45 ℃, the pressure is about 0.3Mpa, the operation temperature of an alkali liquor regeneration tower is 55-60 ℃, the pressure is 0.15Mpa, all stripping gases are nitrogen, the sodium mercaptan content in regenerated alkali liquor is 50-60 mug/g, the disulfide content is 5-10 mug/g, and the total sulfur of refined liquefied gas is 15-20mg/Nm3The disulfide recovery is about 40 tons per year and about 89%.
In conclusion, by means of the technical scheme, the method and the device for efficiently oxidizing the desulfurized alcohol alkali liquor and recovering the disulfide adopt a packed tower air catalytic oxidation technology, the alkali liquor oxidation retention time is only 1/3-1/2 of the volume of an oxidation tower of an empty tower microbubble technology, the sodium mercaptan oxidation efficiency can reach more than 95%, the alkali liquor after oxidation is subjected to multiple coalescence and separation by a hydrophilic filter screen coalescer and a lipophilic filter screen coalescer, the disulfide recovery rate can reach 85-95%, the alkali liquor after disulfide separation is subjected to air stripping and nitrogen two-stage air stripping by a packed tower to remove residual disulfide, the disulfide content in regenerated alkali liquor can be removed to be below 10 mu g/g, the sodium mercaptan content is below 100 mu g/g, and meanwhile, the nitrogen stripping can reduce the dissolved oxygen in the alkali liquor to be below 1mg/L, so as to avoid the problem that mercaptan cannot be removed because mercaptan is directly oxidized into disulfide when regenerated alkali liquor containing dissolved oxygen is recycled for removing mercaptan from liquid hydrocarbon.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The device for efficiently oxidizing sweetening alkali liquor and recovering disulfide is characterized by comprising an alkali liquor oxidation tower (1), wherein the bottom of the alkali liquor oxidation tower (1) is connected with a sweetening alkali liquor line (21), the top of the alkali liquor oxidation tower (1) is connected with a tail gas line (23), one side of the alkali liquor oxidation tower (1) is connected with the upper part of an alkali liquor regeneration tower (12) through an alkali liquor oxidation line (25), the bottom of the alkali liquor regeneration tower (12) is connected with a regenerated alkali liquor line (28), and the top of the alkali liquor regeneration tower (12) is connected with the tail gas line (23);
the alkali liquor oxidation tower (1) is divided into an upper section and a lower section, the upper section is a separation section, the lower section is an oxidation section, a tail gas disulphite removal coalescer (2) is installed at the top of the separation section, a disulphite separation tank (4) is arranged below the tail gas disulphite removal coalescer (2), the inner tower wall of the disulphite separation tank (4) is connected with a disulphite line (24), a disulphite dealkali coalescer (5) is arranged below the disulphite separation tank (4), a baffle (7) is arranged below the disulphite dealkali coalescer (5), the inner tower wall of the baffle (7) is connected with an alkali liquor oxidation line (25), a disulphite dealkali coalescer (3) is arranged in the disulphite separation tank (4), and an alkali liquor disulphite removal coalescer (6) is arranged in; an alkali liquor oxidation tower filler (8) is installed in the oxidation section, an alkali liquor oxidation tower air distributor (9) is arranged below the alkali liquor oxidation tower filler (8), and the alkali liquor oxidation tower air distributor (9) is connected with an oxidation air line (22);
a first alkali liquor regeneration tower filler (13) is arranged below an alkali liquor inlet at the upper part of the alkali liquor regeneration tower (12), an air distributor (14) of the alkali liquor regeneration tower is arranged below the first alkali liquor regeneration tower filler (13), the air distributor (14) of the alkali liquor regeneration tower is connected with an air stripping air line (26), a second alkali liquor regeneration tower filler (15) is arranged below the air distributor (14) of the alkali liquor regeneration tower, a nitrogen distributor (16) of the alkali liquor regeneration tower is arranged below the second alkali liquor regeneration tower filler (15), and the nitrogen distributor (16) of the alkali liquor regeneration tower is connected with an air stripping nitrogen line (27);
the desulfurization alcohol alkali liquor line (21) is provided with a catalyst injector (10), the oxidation alkali liquor line (25) is provided with an alkali liquor heater (11), and the regeneration alkali liquor line (28) is provided with an alkali liquor cooler (17).
2. An apparatus for efficient oxidation and disulfide recovery from a sweetening lye according to claim 1, characterized in that the screens in the off-gas and lye disulfide coalescers (2, 6) are both oleophilic materials and the screen size in the off-gas and lye disulfide coalescers (2, 6) are both 5-15 μm.
3. The device for high-efficiency oxidation and disulfide recovery of sweetening alkali liquor according to claim 2, characterized in that the filter screens in the tail gas sweetening coalescer (2) and the lye sweetening coalescer (6) adopt blend modified fiber filaments of polythioether and fluoropolymer or stainless steel fiber filaments with the surfaces coated with blend of polythioether and fluoropolymer, the longitudinal and transverse fiber filaments are welded by hot melting without adhesive, and the wetting angle of the surface oil of the fiber filaments is not more than 3 degrees.
4. The device for high-efficiency oxidation and disulfide recovery of a mercaptan-removed lye as claimed in claim 1, wherein the filter screens in said first disulfide dealkalizing coalescer (3) and said second disulfide dealkalizing coalescer (5) are both stainless steel microfilaments with hydrophilically modified surfaces, the wetting angle of the surface water of the stainless steel microfilaments is not more than 3 degrees, and the pore size of the filter screens in said first disulfide dealkalizing coalescer (3) and said second disulfide dealkalizing coalescer (5) is 5-15 μm.
5. The device for efficiently oxidizing and recovering the disulfide by the mercaptan-removed alkali liquor according to claim 1, wherein 4-8 alkali liquor holes are uniformly distributed at the bottom of the disulfide separation tank (4), the pore diameter of the alkali liquor holes is 2-5mm, and the alkali liquor oxidation tower packing (8), the alkali liquor regeneration tower packing I (13) and the alkali liquor regeneration tower packing II (15) are all stainless steel regular packing or random packing.
6. The device for efficiently oxidizing and recovering disulfide from a sweetening alkali liquor according to claim 1, wherein the diameter of the separation section is 1.2-1.5 times of the diameter of the oxidation section, the ratio of the inner diameter of the disulfide separation tank (4) to the diameter of the oxidation section and the ratio of the inner diameter of the baffle (7) to the diameter of the oxidation section are not less than 0.8, the ratio of the height of the separation section to the height of the oxidation section is 0.3-0.6, the ratio of the height to the diameter of the oxidation section is 4-8, and the ratio of the height to the diameter of the alkali liquor regeneration tower (12) is 6-10.
7. A method for oxidation of a desulfurized alcohol lye and recovery of disulfides using the apparatus of claim 1 comprising the steps of:
s1, the mercaptan removal alkali liquor with the temperature of 30-45 ℃ enters an alkali liquor oxidation tower (1) from the bottom of the tower, the operation pressure at the top of the alkali liquor oxidation tower (1) is 0.2-0.5MPa, and an alkali liquor oxidation catalyst is continuously or discontinuously added into the alkali liquor through a catalyst injector (10) so that the catalyst concentration in the alkali liquor is 200 mug/g;
s2 compressed air is uniformly distributed on the cross section in the tower through an air distributor (9) of the alkali liquor oxidation tower, alkali liquor and air bubbles are sheared and fully contacted by a filler (8) of the alkali liquor oxidation tower in the process of rising in the alkali liquor oxidation tower (1), sodium mercaptan in the alkali liquor is oxidized into sodium hydroxide and disulfide, the alkali liquor carried by the disulfide continuously floats up along with the air bubbles, the alkali liquor carried by the disulfide settles at the lower layer, the interface level of the disulfide and the alkali liquor is controlled between the top of a baffle plate (7) and the bottom of a disulfide dealkalization coalescer II (5), when the alkali liquor overflows the baffle plate (7) and passes through the alkali liquor dealkalization coalescer (6), the emulsified disulfide tiny droplets are aggregated into large disulfide droplets and float to a disulfide layer, and the alkali liquor after the disulfide is aggregated and separated sinks and is pumped to an alkali liquor regeneration tower (12) through an oxidized alkali liquor line (25);
s3, when the disulfide carrying the alkali liquor floats upwards along with the bubbles and passes through a disulfide dealkalization coalescer II (5), the emulsified alkali liquor tiny droplets are aggregated into large alkali liquor droplets and sink to an alkali liquor layer, the disulfide continuously floats upwards with the tail gas and is separated in a tail gas section, and the liquid level of the disulfide is controlled above a disulfide separation tank (4); when the disulfide enters the disulfide separation tank (4), micro-emulsified alkali liquor micro droplets contact the disulfide dealkalization coalescer I (3) to be coalesced into large alkali liquor droplets and sink to the bottom of the disulfide separation tank (4), and the large alkali liquor droplets continue to sink to an alkali liquor layer through an alkali liquor hole at the bottom of the disulfide separation tank (4); when the tail gas passes through a tail gas disulfide removal coalescer (2) at the top of the alkali liquor oxidation tower (1), small disulfide drops in the tail gas are gathered into large drops and drop to a disulfide layer; the disulfide is discharged through a disulfide line (24) connected in the disulfide separation tank (4); the tail gas for separating the disulfide is discharged through a tail gas line (23) at the top of the alkali liquor oxidation tower (1);
s4 heating the alkali liquor from the alkali liquor oxidation tower (1) to 50-65 ℃ by the alkali liquor heater (11), feeding the heated alkali liquor into the alkali liquor regeneration tower (12) from the upper side, sequentially carrying out air stripping twice by two sections of fillers and air and nitrogen from top to bottom, uniformly distributing the compressed air and nitrogen on the cross section in the tower through the air distributor and the nitrogen distributor in the alkali liquor regeneration tower (12), enabling the alkali liquor and bubbles to reversely flow in the alkali liquor regeneration tower (12), shearing and fully contacting the fillers in the tower, and dissolving residual disulfide in the alkali liquor in the bubbles and taking away the disulfide along with tail gas; stripping the bottom layer nitrogen gas and simultaneously removing dissolved oxygen in the alkali liquor; discharging the disulfide-containing tail gas from the top of the alkali liquor regeneration tower (12); the regenerated alkali liquor is discharged from a regenerated alkali liquor line (28) at the bottom of the alkali liquor regeneration tower (12).
8. The method for oxidizing sweetening alcohol lye and recovering disulfides of claim 7 wherein the lye oxidation catalyst is sulfonated cobalt phthalocyanine or ammonium cobalt phthalocyanine sulfonate.
9. The method for oxidizing sweetening alcohol lye and recovering disulfide according to the claim 7, characterized in that the lye retention time in the packing section of the lye oxidation tower (1) in the step S1 is 1-4 hours, the operation temperature of the lye oxidation tower (1) is controlled at 30-45 ℃, and the air flow in the step S2 is 1.5-2.5 times of the air flow needed by the theoretical calculation of the total oxidation of sodium alcoholate in the sweetening alcohol lye.
10. The method for oxidizing desulfurized alcohol lye and recovering disulfides as set forth in claim 7 wherein in step S4 the single-stage packing lye retention time of the lye regeneration tower (12) is 0.2-0.6 hours, the operating temperature of the lye regeneration tower (12) is controlled at 50-65 ℃, the gas-liquid ratio of the stripping air is 10-30:1, and the gas-liquid ratio of the stripping nitrogen is 5-10: 1.
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