CN113877405B - Waste lubricating oil hydrogenation gas treatment and discharge process - Google Patents
Waste lubricating oil hydrogenation gas treatment and discharge process Download PDFInfo
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- CN113877405B CN113877405B CN202111392874.2A CN202111392874A CN113877405B CN 113877405 B CN113877405 B CN 113877405B CN 202111392874 A CN202111392874 A CN 202111392874A CN 113877405 B CN113877405 B CN 113877405B
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- 238000005984 hydrogenation reaction Methods 0.000 title claims abstract description 61
- 238000000034 method Methods 0.000 title claims abstract description 42
- 230000008569 process Effects 0.000 title claims abstract description 40
- 239000002699 waste material Substances 0.000 title claims abstract description 28
- 239000010687 lubricating oil Substances 0.000 title claims abstract description 22
- 239000007789 gas Substances 0.000 claims abstract description 128
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 68
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims abstract description 54
- 239000003546 flue gas Substances 0.000 claims abstract description 54
- 230000009615 deamination Effects 0.000 claims abstract description 51
- 238000006481 deamination reaction Methods 0.000 claims abstract description 51
- 239000003054 catalyst Substances 0.000 claims abstract description 26
- 238000002485 combustion reaction Methods 0.000 claims abstract description 26
- 230000003009 desulfurizing effect Effects 0.000 claims abstract description 20
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 10
- 230000001172 regenerating effect Effects 0.000 claims abstract description 6
- 238000006477 desulfuration reaction Methods 0.000 claims description 47
- 230000023556 desulfurization Effects 0.000 claims description 47
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 40
- 229910052717 sulfur Inorganic materials 0.000 claims description 34
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- 229910052739 hydrogen Inorganic materials 0.000 claims description 30
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 28
- 239000011593 sulfur Substances 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 26
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 25
- 230000008929 regeneration Effects 0.000 claims description 25
- 238000011069 regeneration method Methods 0.000 claims description 25
- 239000002131 composite material Substances 0.000 claims description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 229910021529 ammonia Inorganic materials 0.000 claims description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 238000001179 sorption measurement Methods 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 238000004383 yellowing Methods 0.000 claims description 12
- 230000018044 dehydration Effects 0.000 claims description 11
- 238000006297 dehydration reaction Methods 0.000 claims description 11
- 150000002431 hydrogen Chemical class 0.000 claims description 11
- 239000001301 oxygen Substances 0.000 claims description 11
- 238000007599 discharging Methods 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000741 silica gel Substances 0.000 claims description 8
- 229910002027 silica gel Inorganic materials 0.000 claims description 8
- 238000010521 absorption reaction Methods 0.000 claims description 7
- 238000010926 purge Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 6
- 239000011148 porous material Substances 0.000 claims description 6
- CSDREXVUYHZDNP-UHFFFAOYSA-N alumanylidynesilicon Chemical compound [Al].[Si] CSDREXVUYHZDNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 5
- 229910002651 NO3 Inorganic materials 0.000 claims description 4
- 238000010668 complexation reaction Methods 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims description 3
- 150000004706 metal oxides Chemical class 0.000 claims description 3
- 239000012716 precipitator Substances 0.000 claims description 3
- 239000000376 reactant Substances 0.000 claims description 2
- 230000001502 supplementing effect Effects 0.000 claims description 2
- 238000000746 purification Methods 0.000 abstract description 10
- 230000008901 benefit Effects 0.000 abstract description 9
- 239000007788 liquid Substances 0.000 abstract description 6
- 238000007664 blowing Methods 0.000 abstract description 3
- 239000013589 supplement Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 description 37
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 10
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000002156 mixing Methods 0.000 description 9
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000005260 corrosion Methods 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000003921 oil Substances 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000010779 crude oil Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 238000012545 processing Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 238000009825 accumulation Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- KAEAMHPPLLJBKF-UHFFFAOYSA-N iron(3+) sulfide Chemical compound [S-2].[S-2].[S-2].[Fe+3].[Fe+3] KAEAMHPPLLJBKF-UHFFFAOYSA-N 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 1
- YZCKVEUIGOORGS-NJFSPNSNSA-N Tritium Chemical compound [3H] YZCKVEUIGOORGS-NJFSPNSNSA-N 0.000 description 1
- 239000000443 aerosol Substances 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000002199 base oil Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- LDHBWEYLDHLIBQ-UHFFFAOYSA-M iron(3+);oxygen(2-);hydroxide;hydrate Chemical compound O.[OH-].[O-2].[Fe+3] LDHBWEYLDHLIBQ-UHFFFAOYSA-M 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 239000002480 mineral oil Substances 0.000 description 1
- 235000010446 mineral oil Nutrition 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- -1 nitrogen-containing compound Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- HYHCSLBZRBJJCH-UHFFFAOYSA-M sodium hydrosulfide Chemical compound [Na+].[SH-] HYHCSLBZRBJJCH-UHFFFAOYSA-M 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
Classifications
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- 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
- B01D53/81—Solid phase processes
- B01D53/82—Solid phase processes with stationary reactants
-
- 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
- B01D53/26—Drying gases or vapours
- B01D53/261—Drying gases or vapours by adsorption
-
- 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
- B01D53/46—Removing components of defined structure
- B01D53/48—Sulfur compounds
- B01D53/52—Hydrogen sulfide
-
- 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
- B01D53/46—Removing components of defined structure
- B01D53/54—Nitrogen compounds
- B01D53/58—Ammonia
-
- 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
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8625—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/16—Hydrogen
-
- 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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
The invention discloses a waste lubricating oil hydrogenation gas treatment and discharge process. The hydrogenation gas adopts three towers connected in series to remove H respectively 2 S、NH 3 And H 2 O. First removing H 2 S is added with a secondary line to supplement H to the hydrogenation gas to protect the renewable deamination agent Cu/HZSM-5 2 S protects the hydrogenation catalyst in a vulcanized state; the desulfurizing agent is used as a gas mercury removing agent. The deamination agent outlet is subjected to heat H after exceeding the standard 2 Blowing and regenerating, wherein the regenerated gas is sent to a combustion furnace, and the burned flue gas enters a double-layer denitration purification tower and is discharged. The process does not produce waste liquid and NH 3 Secondary pollution is caused, and economic and social benefits are obvious.
Description
Technical Field
The invention relates to a waste lubricating oil hydrogenation gas treatment and discharge process, and belongs to the field of petrochemical industry.
Background
The department of industrial and medical science 1 month 2016 issued "industrial and medical standards for comprehensive utilization of waste mineral oil" and encouraged the use of hydrofining technology. In recent years, the hydrofining technology of the waste lubricating oil has been paid more attention to higher environmental protection, economy and operability, the quality and quality of products can be obviously improved through the hydrofining technology, the hydrofining technology is a main stream technology for regenerating the waste lubricating oil in view of the requirements of product quality and processing environmental protection, and the hydrofining process for obtaining high-quality base oil becomes one of the indispensable links in the regeneration process of the waste lubricating oil.
Typically, after hydrofining, hydrocracking, catalytic cracking of refinery oils, sulfur-containing compounds are converted to H 2 S, converting the nitrogen-containing compound into ammonia. After the acid sewage obtained by water-cooling washing the sulfur-containing and ammonia-containing waste gas is recovered and stripped, H 2 S is led to a Claus sulfur recovery device from the top of the stripping tower, NH 3 Leading out from the middle of the tower, cooling and separating water to prepare a liquid ammonia product. The process flow is complex, the investment is large, the energy consumption is high, and the method cannot be applied to small and medium-sized hydrogenation enterprises and is difficult to be used for the waste lubricating oil hydrogenation gas treatment.
Patent CN103432902A, CN1109020A, CN101186280A, CN103130195a discloses a process for producing sodium hydrosulfide by absorbing and utilizing hydrogen sulfide in tail gas, most of the processes are complex, the impurity content of the product is high, waste liquid can be produced, and the economic benefit and the social benefit are not ideal.
H in gas is removed by adopting fixed bed dry desulfurization process 2 S, the process is simple, no waste liquid pollution is caused, the processing capacity is small, and the desulfurizing agent is difficult to regenerate. Iron oxide (Fe) 2 O 3 ) The alpha and gamma hydrates of (a) have a desulphurisation effect and react with hydrogen sulphide as follows:
Fe 2 O 3 ·H 2 O + 3 H 2 S = Fe 2 S 3 · H 2 O + 3H 2 O (1)
Fe 2 O 3 ·H 2 O + 3 H 2 S =2FeS + S + 4H 2 O (2)
when the desulfurizing agent is alkaline, the desulfurizing reaction is carried out according to the formula (1); when the desulfurizing agent is acidic neutral, the desulfurizing reaction is carried out as in (2).
In the presence of an alkaline water film, the desulfurization reaction is generally carried out by the following processes:
(1) the hydrogen sulfide molecules diffuse to the surface of the iron oxide hydrate through a gas film on the gas-solid interface.
(2) Through the pores of the desulfurizing agent.
(3) Hydrogen sulfide dissolves in the water film on the surface of iron oxide and dissociates into HS - 、S 2- Ions.
④HS - 、S 2- Lattice Oxygen (OH) of ion and hydrated ferric oxide - 、O 2- ) Mutually replace to generate
Fe 2 S 3 · H 2 O。
(5) Lattice rearrangement, transformation of needle-shaped and cube-shaped structures of hydrated iron oxide into hydrated iron sulfide
Monoclinic crystals.
(6) The generated surface layer ferric sulfide and the inner layer ferric oxide perform interface reaction, and sulfur diffuses inwards.
(7) After surface renewal, the surface iron oxide continues to absorb hydrogen sulfide.
In the presence of oxygen, the generated ferric sulfide generates oxidation reaction to separate out sulfur, and the reaction is called
For regeneration. The reaction is as follows:
Fe 2 S 3 · H 2 O +O 2 =Fe 2 O 3 ·H 2 O +3S (3)
FeS + O 2 = Fe 2 O 3 ·H 2 O +2S (4)
the regeneration reaction according to the formula (3) is fast and thorough, whereas the regeneration reaction according to the formula (4) is difficult to be performed at normal temperature, and not only is the reaction speed slow, but also the regeneration is incomplete. Therefore, the desulfurization reaction should be performed under alkaline conditions, so that the reaction of the formula (4) is avoided as much as possible. If the catalyst is used for the hydrodesulfurization of waste lubricating oil, the problems to be solved mainly have two points: firstly, the desulfurizing agent is repeatedly regenerated, so that sulfur is accumulated, holes are blocked, and the accumulated sulfur capacity is reduced; secondly, the disposal problem of the desulfurizing agent after use.
Patent CN1894019a discloses a method of treating an ammonia-containing gas in order to purify the gas. Let a part of NH 3 Catalytic oxidation to NO, the resulting NO and NH 3 O and O 2 The reaction produced nitrogen. The process has high running cost, NO pollution caused by poor control and NO economic benefit.
NH 3 The combustion gives off a great deal of heat, and the following chemical reactions occur:
NH 3 (g)+0 2 (g)=NO 2 (g)+ />H 2 0 ΔH = -316.25kg/mol （5）
NH 3 (g) +O 2 (g) = /> N 2 (g) + /> H 2 O ΔH = -382.6kJ/mol （6）
if used for treating NH in waste lubricating oil hydrogenation gas 3 To solve NH 3 Is enriched in NO generated after combustion 2 Is a removal problem.
The waste lubricating oil processing industry is limited by raw material collection and purchase, most enterprises with the scale of 3-10 ten thousand tons/year, and the hydrogenation gas treatment and discharge process with obvious economic benefit and social benefit without generating waste liquid is urgently needed under the dual pressure of environmental protection and benefit so as to solve the urgent need.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention provides a waste lubricating oil hydrogenation gas treatment and discharge process, and the hydrogenation gas adopts three towers to respectively remove H in series 2 S、NH 3 And H 2 O. First removing H 2 S is added with a secondary line to supplement H to the hydrogenation gas to protect the renewable deamination agent Cu/HZSM-5 2 S protects the hydrogenation catalyst in a vulcanized state; the desulfurizing agent is used as a gas mercury removing agent. The deamination agent outlet is subjected to heat H after exceeding the standard 2 Blowing and regenerating, wherein the regenerated gas is sent to a combustion furnace, and the burned flue gas enters a double-layer denitration purification tower and is discharged.
The invention is realized by the following technical scheme:
the process for treating and discharging the waste lubricating oil hydrogenation gas is characterized by comprising the following steps of:
firstly, mostly entering a desulfurization reactor, wherein H in the gas 2 S reacts with active components of the desulfurizing agent, H 2 S is removed, H in the gas after desulfurization 2 S is less than 0.03mg/m 3 ；
The hydrogenated gas subjected to desulfurization enters a deamination reactor, and NH in the gas 3 Low-temperature complexation adsorption reaction is carried out on the ammonia-removing agent and active components, the ammonia-removing agent is converted into corresponding complex, and NH in the gas after ammonia removal 3 Less than 3mg/m 3 The single ammonia capacity of the deamination agent is up to 10%;
feeding the hydrogenated gas subjected to desulfurization and deamination into a dehydration adsorption tower to remove H 2 If the content of the non-hydrogen gas in the tower outlet gas of O is lower than 35%, the tower outlet gas is mixed with a small part of hydrogenation gas which does not enter a desulfurization and deamination reactor and new hydrogen, and then enters a hydrogenation circulation system to remove H 2 If the content of the non-hydrogen gas in the tower outlet gas of O is higher than 35%, the tower outlet gas is discharged to a combustion furnace, and the flue gas after combustion is directly exhausted due to no sulfur or no nitrate, at the moment, a small part of the flue gas does not enterThe hydrogenation gas of the desulfurization and deamination reactor is mixed with new hydrogen and then enters a hydrogenation circulation system;
the deamination agent outlet is higher than 3mg/m 3 By heat H 2 Blowing and regenerating, wherein the regenerated gas is sent to a combustion furnace, and the burned flue gas enters a double-layer denitration purification tower and is discharged.
The active component of the desulfurizing agent is NH 4 HCO 3 Fe-Ce composite oxide prepared by precipitator and capable of resisting ammonia and efficiently removing H 2 S, S. Desulfurization outlet H 2 S is higher than 0.03mg/m 3 And then introducing nitrogen and oxygen with the oxygen content of 1% -5% for regeneration, wherein the regeneration temperature is 30 ℃ -50 ℃, the desulfurizing agent after 3-5 times of regeneration is a sulfur-carrying 55% -65% composite oxide, and discharging the sulfur-carrying composite oxide to be used as a gas mercury removing agent.
The deamination agent is a renewable deamination agent Cu/HZSM-5, the carrier is an HZSM-5 molecular sieve with a silicon-aluminum ratio of 25-50 and a pore volume of 0.21 mL/g-0.32 mL/g.
The dehydration adsorption tower is filled with silica gel, the water absorption capacity is 30% -35%, and after the water absorption fails, the air speed is 300 h at 110 ℃ -150 DEG C -1 ~3000h -1 And (3) continuing to use after nitrogen purging.
The mixed gas entering the hydrogenation circulation system is H 2 S content of 2mg/m 3 ~6mg/m 3 。
Said heat H 2 The temperature is 160-240 ℃ and the airspeed is 500h -1 ~2000h -1 。
The upper layer of the double-layer denitration purifying tower is filled with a flue gas denitration catalyst, the lower layer is filled with a flue gas denitration agent, and gas enters from below and goes out from above.
The flue gas denitration catalyst filled in the upper layer of the double-layer denitration purifying tower is composite metal oxide, and the temperature is 120-320 ℃ and the airspeed is 2000h -1 ～6000 h -1 Under the condition, NO reacts with CO to generate N 2 The conversion rate of the catalyst is more than or equal to 99.0 percent.
The flue gas de-yellowing agent filled in the lower layer of the double-layer denitration purifying tower is Cu/C, wherein active carbon is both a carrier and a reactant, and the temperature is 120-320 ℃ and the airspeed is 2000h -1 ～6000 h -1 Next, for NO 2 The removal rate of the catalyst is more than or equal to 99.5 percent.
Two feed inlets are arranged at the upper part of the lower layer of the double-layer denitration purifying tower, and the flue gas yellowing agent consumed by the reaction is fed intermittently.
The invention has the beneficial effects that:
h in gas is removed by adopting fixed bed dry desulfurization process 2 S, the process is simple, and no waste liquid pollution is caused. As previously described, NH in Hydrogen 3 Providing a suitable Fe 2 O 3 The invention aims at the problems of sulfur accumulation, hole blocking, accumulated sulfur capacity reduction and disposal of the desulfurizer after use caused by repeated regeneration of common ferric oxide desulfurizer in the alkaline environment of deoxidation and regeneration 4 HCO 3 Fe-Ce composite oxide prepared by precipitator and capable of resisting ammonia and efficiently removing H 2 S, S. According to research, the Ce can be added to uniformly disperse sulfur microcrystals, so that hole blocking and sulfur aggregation can be effectively avoided, the composite oxide can be regenerated for 3-5 times, the sulfur carrying amount is up to 55% -65%, and the Fe-Ce composite oxide after uniform sulfur carrying has excellent natural gas mercury removal activity, high mercury removal precision and long-period use. The development of the desulfurizer with high accumulated sulfur capacity and sustainable use enables the invention to adopt a fixed bed dry desulfurization process in a free margin, and compared with the conventional processes of water washing, acid water stripping, low-temperature methanol washing and the like, the desulfurizer has the advantages of simple process flow, small investment, low energy consumption and no waste liquid pollution.
NH removal 3 The process has no secondary pollution. Typically due to NH 3 Is dissolved in water to be alkaline, and H is dissolved in the water 2 The process for preparing high-quality and practical liquid ammonia by extracting the S and other acidic water is complex, the high-purity liquid ammonia has strong volatility, and ammonia can escape into air or water from various links from preparation to transportation and application, so that environmental pollution is caused. NH (NH) 3 Is an extremely toxic, polluting, corrosive, irritating and dangerous alkaline gas, which not only affects the physical health of people and even endangers life safety, but also generates aerosol and tiny particles in the atmosphere, and is an important reason for PM2.5 formation. The invention adopts the renewable deamination agent Cu/HZSM-5, and the fixed bed is used for low-temperature complexation and NH adsorption 3 Converting into corresponding complex, deaminizing NH in gas 3 Less than 3mg/m 3 The single ammonia capacity of the deamination agent is up to 10%, and the outlet of the deamination agent is higher than 3mg/m 3 By heat H 2 Purging and regenerating, wherein the regenerated gas is sent to a combustion furnace, and the burned flue gas is discharged after entering a double-layer denitration purification tower, and even in the regeneration process, the concentration of ammonia is lower than 0.5 percent due to larger gas quantity, so that the risk of secondary pollution caused by ammonia escape is small compared with the conventionally treated liquid ammonia.
Through fine removal of H 2 S is supplemented with H 2 S, respectively protecting the deamination agent and the hydrogenation catalyst in a vulcanized state. The regenerable deamination agent is Cu/HZSM-5 and has excellent H 2 S is removed in activity, and active component Cu after desulfurization loses low-temperature complexation adsorption NH 3 And the desulfurization reaction is irreversible, therefore, the invention adopts Fe-Ce composite oxide to carry out fine H removal 2 S, H in the desulfurized gas 2 S is less than 0.03mg/m 3 The deamination agent is protected from sulfur poisoning. In addition, the active components of the hydrogenation catalyst are Mo, W, co, ni in a vulcanized state, and H in the hydrogenation gas 2 S is too low, so that the active components in the vulcanized state are reversely vulcanized, the catalytic activity is reduced, and the service life is shortened. The invention designs a secondary line for supplementing H to the hydrogenation gas 2 S, H in the mixed gas entering the hydrogenation circulation system 2 S content of 2mg/m 3 ~6mg/m 3 Thereby protecting the hydrogenation catalyst in the sulfided state.
After combustion, the flue gas does not need to be desulfurized, and after purification by adopting a double-layer denitration tower, the flue gas is sulfur-free and low in nitrate. The process comprises two gas treatment steps, namely, the hot hydrogen is treated by a combustion furnace, namely, the regenerated gas of a deamination reactor, and the H is removed 2 S、NH 3 And H 2 After O, the non-hydrogen gas is higher than 35% of the hydrogenation gas, and H is 2 S is less than 0.03mg/m 3 Thus, the flue gas after combustion is almost free of SO 2 And the flue gas desulfurization operation is omitted. The upper layer of the double-layer denitration purifying tower is filled with the flue gas denitration catalyst, the lower layer is filled with the flue gas denitration agent, gas enters from bottom to top, the flue gas firstly contacts with the Cu/C flue gas denitration agent filled in the lower layer, and the temperature is 120-320 ℃ and the airspeed is 2000h -1 ～6000 h -1 The smoke is more than 99.5 percent of NO 2 Is removed to finish the process of 'in the flue gas'Removing yellow smoke, enabling generated NO to enter the upper layer of a denitration tower along with smoke, and filling the smoke denitration catalyst which is composite metal oxide at the temperature of 120-320 ℃ and the airspeed of 2000h -1 ～6000 h -1 Under the condition, NO reacts with CO to generate N 2 The conversion rate of the flue gas is more than or equal to 99.0 percent, and the NOx in the flue gas purified by the double-layer denitration tower is lower than the emission standard.
And pollution and corrosion are reduced as much as possible, and the operation cost is low. After conventional hydrogenation gas purification, H 2 S adopts a Claus device to prepare sulfur, and is rich in H 2 H in S gas 2 S concentration is up to 40%, and the process flow is complex and high in H content 2 S can cause serious pollution and corrosion to the stripped pipe fitting and the tower body; conventional removal and utilization of NH in hydrogen addition 3 The process is to prepare high-purity liquid ammonia products, and the corrosion equipment also pollutes the environment. The invention adopts a dry fixed bed desulfurization deamination route with simple process and low cost, so that H is contained 2 S、NH 3 The gas passes through the least equipment, valves and pipelines, H in the gas treatment process 2 S、NH 3 The concentration of the gas is low, and the pollution and corrosion of equipment are reduced. The dry fixed bed process is simple to operate, and the running cost of the device is effectively reduced.
Green economy. The desulfurizing agent is used in a high-accumulation sulfur capacity way, and discharged after desulfurization is continuously used as a natural gas mercury removing agent with excellent performance. The deamination regenerated gas is combusted, heat is used for heating, the flue gas is sulfur-free, the Huang Yan and NOx are removed by a double-layer denitration purifying tower device until the NOx is lower than the emission standard, and sulfur-free low-nitrate emission is achieved. The whole waste lubricating oil hydrogenation gas treatment and discharge process has low investment cost and obvious economic and social benefits.
Drawings
FIG. 1 is a flow chart of a waste lubricating oil hydrogenation gas treatment and discharge process.
In the figure, a desulfurization reactor 1, a deamination reactor 2, a dehydration adsorption tower 3, a combustion furnace 4 and a double-layer denitration purification tower 5 are adopted.
Detailed Description
The present invention will now be described in further detail with reference to the drawings and specific embodiments, but the manner in which the same are provided is by way of illustration only and should not be construed to limit the scope of the invention.
Example 1
In the Henan of the project of 3 ten thousand tons/year of waste lubricating oil hydrogenation, the total sulfur of raw material crude oil is 3000ppm and the total nitrogen is 500ppm. The space velocity of the hydrogenation catalyst is 0.3h -1 (packing 13 m) 3 ) Hydrogen to oil ratio 800:1, circulating hydrogen amount 3080Nm 3 And/h, the total sulfur in the added hydrogen is 3.33gS/m 3 Total nitrogen of 0.56g/m 3 The water vapor content was 0.03%, and the hydrotreated gas discharge process was as shown in FIG. 1. The hydrogenation gas firstly enters a desulfurization reactor 1, and 50m of the hydrogenation gas is filled in the desulfurization reactor 3 Fe-Ce composite oxide, H 2 S reacts with active components of the desulfurizing agent, H 2 S is removed, H in the gas after desulfurization 2 S is less than 0.03mg/m 3 After one month of operation, desulfurization outlet H 2 S is higher than 0.03mg/m 3 Introducing nitrogen and oxygen with oxygen content of 1% for regeneration, wherein the regeneration temperature is 50 ℃, operating for three months, accumulating for regeneration for 3 times, discharging for 50m 3 The composite oxide with 55% sulfur is used as a gas mercury removing agent.
The desulfurized hydrogenated gas enters a deamination reactor 2, and 10m of the hydrogenated gas is filled in the deamination reactor 3 Deamination agent Cu/HZSM-5, its carrier is HZSM-5 molecular sieve with silicon-aluminum ratio of 50 and pore volume of 0.32mL/g, and its operation is half a month, and its outlet is higher than 3mg/m 3 Ammonia capacity of 10%, 160 deg.C, 2000h -1 ，20000 Nm 3 And/h hydrogen regeneration for 20h. The regenerated gas enters a combustion furnace 4 for combustion to generate 65000Nm 3 /h flue gas, wherein NO 2 4600mg/m 3 The flue gas enters a double-layer denitration purification tower 5, and 32.5 m are respectively filled in the lower layer and the upper layer 3 Flue gas de-yellowing agent and 32.5 m 3 The denitration catalyst of (2) has gas inlet and outlet from bottom to top, and the airspeed is 2000h -1 The temperature is 120 ℃, wherein NO is detected at the outlet of the flue gas yellowing agent 2 The NO of the denitration catalyst outlet is 23 mg/m 3 NO reacts with CO to form N 2 The conversion rate of the flue gas is 99.5 percent, and the NOx in the flue gas purified by the double-layer denitration tower is lower than the emission standard. The operation is carried out for three months, two feed inlets are arranged at the upper part of the lower layer of the denitration purifying tower, and 5.4. 5.4 m is supplemented 3 And (3) a flue gas yellowing agent consumed by the reaction.
The hydrogenated gas after desulfurization and deamination enters a dehydration adsorption tower 3, and 27m is filled in the dehydration adsorption tower 3 Silica gel, the water absorption capacity of the silica gel is 30% after 10h of operation, 110 ℃ is introduced, and the airspeed is 3000 h -1 After purging for 1h, the reactor was put into operation. H removal 2 The out-column gas of O and 5.5Nm 3 Per h of hydrogenated gas which did not enter the desulfurization deamination reactor, and 11.3Nm 3 And (3) after mixing the new hydrogen, feeding the mixed hydrogen into a hydrogenation circulation system. Operating for 7H, removing H 2 The non-hydrogen gas content in the tower outlet gas of O is higher than 35 percent, and the tower outlet gas is discharged to a combustion furnace, and the flue gas is directly exhausted after the combustion, at the moment, 5.5Nm 3 Hydrogenated gas which does not enter into desulfurization and deamination reactor per hour and 3075Nm 3 After mixing the hydrogen, the mixture enters a hydrogenation circulation system and enters a mixed gas of the hydrogenation circulation system, H 2 S content is 6mg/m 3 Recovering H removal after 1H 2 The out-column gas of O and 5.5Nm 3 Per h of hydrogenated gas which did not enter the desulfurization deamination reactor, and 11.3Nm 3 And (3) after mixing the new hydrogen, entering a hydrogenation circulation system for operation.
Example 2
In the hydrogenation project of waste lubricating oil of 10 ten thousand tons/year in Hubei, the total sulfur of raw material crude oil is 1800ppm and the total nitrogen is 320ppm. . The space velocity of the hydrogenation catalyst is 0.35h -1 (packing 33 m) 3 ) Hydrogen to oil ratio of 700:1, recycle hydrogen flow of 7990Nm 3 And/h, the total sulfur in the added hydrogen is 2.57gS/m 3 Total nitrogen of 0.45g/m 3 The water vapor content was 0.01%, and the hydrotreated gas discharge process was as shown in FIG. 1. The hydrogenation gas firstly enters a desulfurization reactor 1, and is filled with 60m 3 Fe-Ce composite oxide, H 2 S reacts with active components of the desulfurizing agent, H 2 S is removed, H in the gas after desulfurization 2 S is less than 0.03mg/m 3 After 12 days of operation, desulfurization outlet H 2 S is higher than 0.03mg/m 3 Introducing 5% nitrogen and oxygen to regenerate, wherein the regeneration temperature is 30 ℃, operating for two months, accumulating regeneration for 5 times, discharging for 60m 3 The composite oxide with 65% sulfur is used as a gas mercury removing agent.
The desulfurized hydrogenated gas enters a deamination reactor 2, and 40m of the desulfurized hydrogenated gas is filled in the deamination reactor 3 Deamination agent Cu/HZSM-5, its carrier is HZSM-5 molecular sieve with 25 silicon-aluminum ratio and pore volume of 0.21mL/g, and it is operated for 27 days, and exportedHigher than 3mg/m 3 Ammonia capacity of 10%, 200 deg.C, 500h -1 ，20000 Nm 3 And/h hydrogen regeneration for 28h. The regenerated gas enters a combustion furnace 4 for combustion to generate 65000Nm 3 /h flue gas, wherein NO 2 3285mg/m 3 The flue gas enters a double-layer denitration purification tower 5, and the lower layer and the upper layer are respectively filled with 16 m 3 Flue gas de-yellowing agent and 16 m 3 The denitration catalyst of (2) has gas inlet and outlet from bottom to top, and the airspeed is 4000 h -1 The temperature is 320 ℃, wherein NO is detected at the outlet of the flue gas yellowing agent 2 The NO at the outlet of the denitration catalyst is 32.8mg/m 3 NO reacts with CO to form N 2 The conversion rate of the flue gas is 99.0 percent, and the NOx in the flue gas purified by the double-layer denitration tower is lower than the emission standard. The operation is carried out for three months, two feed inlets are arranged at the upper part of the lower layer of the denitration purifying tower, and 11.4. 11.4 m is supplemented 3 And (3) a flue gas yellowing agent consumed by the reaction.
The hydrogenated gas after desulfurization and deamination enters a dehydration adsorption tower 3, and 36m is filled in the dehydration adsorption tower 3 Silica gel, the water absorption of the silica gel is 35% after 20h of operation, 150 ℃ and the airspeed of 300 h are introduced -1 After 2 hours of nitrogen purging, the device is continuously put into use. H removal 2 The off-column gas of O and 6.2Nm 3 Per h of hydrogenated gas which did not enter the desulfurization/deamination reactor, and 23.1Nm 3 And (3) after mixing the new hydrogen, feeding the mixed hydrogen into a hydrogenation circulation system. Operating for 35H, removing H 2 The non-hydrogen gas content in the tower outlet gas of O is higher than 35 percent, and the tower outlet gas is discharged to a combustion furnace, and the flue gas is directly exhausted after the combustion, at the moment, 6.2Nm 3 Hydrogenated gas which does not enter the desulfurization and deamination reactor per hour and 7984Nm 3 After mixing the hydrogen, the mixture enters a hydrogenation circulation system and enters a mixed gas of the hydrogenation circulation system, H 2 S content is 2mg/m 3 Recovering H removal after 1H 2 The off-column gas of O and 6.2Nm 3 Per h of hydrogenated gas which did not enter the desulfurization deamination reactor, 21.3Nm 3 And (3) after mixing the new hydrogen, entering a hydrogenation circulation system for operation.
Example 3
In the Liaoning 6 ten thousand tons/year waste lubricating oil hydrogenation project, the total sulfur of raw material crude oil is 2300ppm and the total nitrogen is 410ppm. . The space velocity of the hydrogenation catalyst is 0.4h -1 (packing 20 m) 3 ) Hydrogen-to-oil ratio of 850:1, and recycle hydrogen volume of 6545Nm 3 And/h, the total sulfur in the added hydrogen is 2.27gS/m 3 Total nitrogen of 0.43g/m 3 The water vapor content was 0.02%, and the hydrotreated gas discharge process was as shown in FIG. 1. The hydrogenation gas firstly enters a desulfurization reactor 1, 45m is filled in 3 Fe-Ce composite oxide, H 2 S reacts with active components of the desulfurizing agent, H 2 S is removed, H in the gas after desulfurization 2 S is less than 0.03mg/m 3 After half a month of operation, desulfurization outlet H 2 S is higher than 0.03mg/m 3 Introducing nitrogen and oxygen with 3% of oxygen for regeneration, wherein the regeneration temperature is 40 ℃, operating for two months, accumulating regeneration for 4 times, discharging 45m 3 The composite oxide with 60 percent of sulfur is used as a gas mercury removal agent.
The desulfurized hydrogenated gas enters a deamination reactor 2, and 35m is filled in the deamination reactor 3 Deamination agent Cu/HZSM-5, its carrier is HZSM-5 molecular sieve with 35 silicon-aluminum ratio and pore volume of 0.27mL/g, and its operation period is one month, and its outlet is above 3mg/m 3 Ammonia capacity of 10%, 200 ℃ and 1500h -1 ，52500 Nm 3 And/h hydrogen regeneration for 48h. The regenerated gas enters a combustion furnace 4 for combustion to generate 131250Nm 3 /h flue gas, wherein NO 2 3254mg/m 3 The flue gas enters a double-layer denitration purification tower 5, and the lower layer and the upper layer are respectively filled with 22 and 22m 3 Is a flue gas de-yellowing agent and 22m 3 The denitration catalyst of (2) has gas inlet and outlet from bottom to top, and the airspeed is 6000 h -1 The temperature is 220 ℃, wherein the outlet NO of the flue gas defluant agent is 2 16.3mg/m 3 ，NO 2 The removal rate of the catalyst is 99.5 percent, and the NO at the outlet of the denitration catalyst is 6.5. 6.5 mg/m 3 NO reacts with CO to form N 2 The conversion rate of the flue gas is 99.8 percent, and the NOx in the flue gas purified by the double-layer denitration tower is lower than the emission standard. The operation is carried out for three months, two feed inlets are arranged at the upper part of the lower layer of the denitration purifying tower, and 8.8 m is supplemented 3 And (3) a flue gas yellowing agent consumed by the reaction.
The hydrogenated gas after desulfurization and deamination enters a dehydration adsorption tower 3, and 35m is filled in the dehydration adsorption tower 3 Silica gel, the water absorption capacity of the silica gel is 34% after 10 hours of operation, 130 ℃ is introduced, and the airspeed is 1600 h -1 After purging for 1.5 hours, the reactor is continuously put into use. H removal 2 The outlet gas of O and 11.5Nm 3 Hydrogenated gas which did not enter desulfurization and deamination reactor per hour and 17.0Nm 3 Hydrogen new per hourAfter mixing, the mixture enters a hydrogenation circulation system. Operating for 24 hours to remove H 2 The non-hydrogen gas content in the tower outlet gas of O is higher than 35 percent, and the tower outlet gas is discharged to a combustion furnace, and the flue gas is directly exhausted after the combustion, at the moment, 11.5Nm 3 Per hour, the hydrogenated gas which does not enter the desulfurization and deamination reactor, and 6534Nm 3 After mixing the hydrogen, the mixture enters a hydrogenation circulation system and enters a mixed gas of the hydrogenation circulation system, H 2 S content is 4mg/m 3 Recovering H removal after 1H 2 The outlet gas of O and 11.5Nm 3 Hydrogenated gas which did not enter desulfurization and deamination reactor per hour and 17.0Nm 3 And (3) after mixing the new hydrogen, entering a hydrogenation circulation system for operation.
Claims (4)
1. The process for treating and discharging the waste lubricating oil hydrogenation gas is characterized by comprising the following steps of:
firstly, mostly entering a desulfurization reactor, wherein H in the gas 2 S reacts with active components of the desulfurizing agent, H 2 S is removed, H in the gas after desulfurization 2 S is less than 0.03mg/m 3 The active component of the desulfurizing agent is NH 4 HCO 3 Fe-Ce composite oxide prepared by precipitator and capable of resisting ammonia and efficiently removing H 2 S, desulfurization outlet H 2 S is higher than 0.03mg/m 3 Then, introducing nitrogen and oxygen with the oxygen content of 1% -5% for regeneration, wherein the regeneration temperature is 30 ℃ -50 ℃, the desulfurizing agent after 3-5 times of regeneration is a sulfur-carrying 55% -65% composite oxide, and discharging the sulfur-carrying composite oxide to be used as a gas mercury removing agent;
the hydrogenated gas subjected to desulfurization enters a deamination reactor, and NH in the gas 3 Low-temperature complexation adsorption reaction is carried out on the ammonia-removing agent and active components, the ammonia-removing agent is converted into corresponding complex, and NH in the gas after ammonia removal 3 Less than 3mg/m 3 The single ammonia capacity of the deamination agent is up to 10%, the deamination agent is a renewable deamination agent Cu/HZSM-5, and the carrier is an HZSM-5 molecular sieve with a silicon-aluminum ratio of 25-50 and a pore volume of 0.21 ml/g-0.32 ml/g;
feeding the hydrogenated gas subjected to desulfurization and deamination into a dehydration adsorption tower to remove H 2 If the content of the non-hydrogen gas in the tower outlet gas of O is lower than 35%, the tower outlet gas is mixed with a small part of hydrogenation gas which does not enter the desulfurization and deamination reactor so as to obtain the catalystAfter being mixed with new hydrogen, the mixture enters a hydrogenation circulation system to remove H 2 If the content of the non-hydrogen gas in the tower gas of O is higher than 35%, the tower gas is discharged to a combustion furnace, and the burned flue gas is directly exhausted due to no sulfur or no nitrate, at the moment, a small part of hydrogenation gas which does not enter a desulfurization and deamination reactor is mixed with new hydrogen and enters a hydrogenation circulation system;
the ammonia gas at the deamination agent outlet is higher than 3mg/m 3 By heat H 2 Purging and regenerating, namely, removing regenerated gas into a combustion furnace, and discharging the burned flue gas after entering a double-layer denitration purifying tower, wherein the upper layer of the double-layer denitration purifying tower is filled with a flue gas denitration catalyst, the lower layer of the double-layer denitration purifying tower is filled with a flue gas denitration agent, the gas enters from bottom to top, the flue gas denitration catalyst filled in the upper layer of the double-layer denitration purifying tower is a composite metal oxide, and the temperature is 120-320 ℃, and the space velocity is 2000h -1 ～6000 h -1 Under the condition, NO reacts with CO to generate N 2 The conversion rate of the catalyst is more than or equal to 99.0 percent, the flue gas yellowing agent filled in the lower layer of the double-layer denitration purifying tower is Cu/C, wherein the activated carbon is both a carrier and a reactant, and the air speed is 2000h at the temperature of 120-320 DEG C -1 ～6000 h -1 Next, for NO 2 The removal rate of the catalyst is more than or equal to 99.5 percent, and the upper part of the lower layer of the double-layer denitration purifying tower is provided with two feed inlets for intermittently supplementing the flue gas yellowing agent consumed by the reaction.
2. The process for treating and discharging waste lubricating oil hydrogenation gas according to claim 1, wherein the dehydration adsorption tower in the step of third step is filled with silica gel, the water absorption capacity is 30% -35%, and after the water absorption is failed, the space velocity is 300 h at 110 ℃ -150 DEG C -1 ~3000h -1 And (3) continuing to use after nitrogen purging.
3. The process for treating and discharging waste lubricating oil hydrogenation gas according to claim 1, wherein the mixture gas entering the hydrogenation circulation system in step iii, H 2 S content of 2mg/m 3 ~6mg/m 3 。
4. The process for the hydrotreatment and discharge of spent lube oil according to claim 1, wherein said hot H is in step i 2 The temperature is 160-240 ℃ and the airspeed is 500h -1 ~2000h -1 。
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| US4391790A (en) * | 1981-09-28 | 1983-07-05 | Standard Oil Company (Indiana) | Method and apparatus for reducing the ammonia concentration of sulfur recovery facility gas streams |
| US5348641A (en) * | 1991-08-15 | 1994-09-20 | Mobil Oil Corporation | Gasoline upgrading process |
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