CN113860265B - System and process for preparing sulfur by efficiently treating alkylated waste acid - Google Patents
System and process for preparing sulfur by efficiently treating alkylated waste acid Download PDFInfo
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- CN113860265B CN113860265B CN202010622401.6A CN202010622401A CN113860265B CN 113860265 B CN113860265 B CN 113860265B CN 202010622401 A CN202010622401 A CN 202010622401A CN 113860265 B CN113860265 B CN 113860265B
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 340
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 296
- 239000011593 sulfur Substances 0.000 title claims abstract description 288
- 239000002699 waste material Substances 0.000 title claims abstract description 168
- 239000002253 acid Substances 0.000 title claims abstract description 113
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 198
- 238000000034 method Methods 0.000 claims abstract description 157
- 230000008569 process Effects 0.000 claims abstract description 127
- 238000006243 chemical reaction Methods 0.000 claims abstract description 87
- 238000011084 recovery Methods 0.000 claims abstract description 69
- 239000000428 dust Substances 0.000 claims abstract description 66
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 62
- 229910052742 iron Inorganic materials 0.000 claims abstract description 34
- 239000007789 gas Substances 0.000 claims description 313
- 238000005984 hydrogenation reaction Methods 0.000 claims description 115
- 239000007788 liquid Substances 0.000 claims description 60
- 125000001741 organic sulfur group Chemical group 0.000 claims description 39
- 238000006460 hydrolysis reaction Methods 0.000 claims description 34
- 230000003197 catalytic effect Effects 0.000 claims description 32
- 230000000694 effects Effects 0.000 claims description 28
- 238000006555 catalytic reaction Methods 0.000 claims description 25
- 230000007062 hydrolysis Effects 0.000 claims description 24
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 230000009471 action Effects 0.000 claims description 16
- 238000010521 absorption reaction Methods 0.000 claims description 15
- 150000001875 compounds Chemical class 0.000 claims description 14
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 12
- 229910052760 oxygen Inorganic materials 0.000 claims description 12
- 239000001301 oxygen Substances 0.000 claims description 12
- 239000002918 waste heat Substances 0.000 claims description 12
- 238000006722 reduction reaction Methods 0.000 claims description 11
- 239000005864 Sulphur Substances 0.000 claims description 10
- 239000006096 absorbing agent Substances 0.000 claims description 9
- 239000003345 natural gas Substances 0.000 claims description 9
- LRDIEHDJWYRVPT-UHFFFAOYSA-N 4-amino-5-hydroxynaphthalene-1-sulfonic acid Chemical compound C1=CC(O)=C2C(N)=CC=C(S(O)(=O)=O)C2=C1 LRDIEHDJWYRVPT-UHFFFAOYSA-N 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 238000010344 co-firing Methods 0.000 claims 1
- 238000005336 cracking Methods 0.000 abstract description 26
- 238000005260 corrosion Methods 0.000 abstract description 8
- 230000007797 corrosion Effects 0.000 abstract description 8
- 231100000572 poisoning Toxicity 0.000 abstract description 5
- 230000000607 poisoning effect Effects 0.000 abstract description 5
- 238000010306 acid treatment Methods 0.000 abstract description 4
- 239000003208 petroleum Substances 0.000 abstract description 3
- 238000012545 processing Methods 0.000 abstract description 2
- TXKMVPPZCYKFAC-UHFFFAOYSA-N disulfur monoxide Inorganic materials O=S=S TXKMVPPZCYKFAC-UHFFFAOYSA-N 0.000 description 41
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical compound S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 41
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 35
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 22
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 17
- 239000003546 flue gas Substances 0.000 description 17
- 238000005804 alkylation reaction Methods 0.000 description 15
- 150000001412 amines Chemical class 0.000 description 15
- 238000002485 combustion reaction Methods 0.000 description 14
- 238000007872 degassing Methods 0.000 description 13
- 239000011148 porous material Substances 0.000 description 13
- 230000029936 alkylation Effects 0.000 description 12
- 238000009833 condensation Methods 0.000 description 11
- 230000005494 condensation Effects 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010791 quenching Methods 0.000 description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 9
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 9
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 9
- 238000001816 cooling Methods 0.000 description 8
- 230000000171 quenching effect Effects 0.000 description 8
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical group [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 7
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 7
- 238000004064 recycling Methods 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 6
- 238000011049 filling Methods 0.000 description 6
- 239000003223 protective agent Substances 0.000 description 6
- 239000012535 impurity Substances 0.000 description 5
- 239000005416 organic matter Substances 0.000 description 5
- 238000010586 diagram Methods 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 239000011814 protection agent Substances 0.000 description 3
- 239000012495 reaction gas Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 2
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 2
- 235000011130 ammonium sulphate Nutrition 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000006229 carbon black Substances 0.000 description 2
- 238000004939 coking Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- RBORURQQJIQWBS-QVRNUERCSA-N (4ar,6r,7r,7as)-6-(6-amino-8-bromopurin-9-yl)-2-hydroxy-2-sulfanylidene-4a,6,7,7a-tetrahydro-4h-furo[3,2-d][1,3,2]dioxaphosphinin-7-ol Chemical compound C([C@H]1O2)OP(O)(=S)O[C@H]1[C@@H](O)[C@@H]2N1C(N=CN=C2N)=C2N=C1Br RBORURQQJIQWBS-QVRNUERCSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000005299 abrasion Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 239000001282 iso-butane Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000019635 sulfation Effects 0.000 description 1
- 238000005670 sulfation reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0413—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the combustion step
- C01B17/0417—Combustion reactors
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D46/0036—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions by adsorption or absorption
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D49/00—Separating dispersed particles from gases, air or vapours by other methods
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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
- B01D53/002—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 by condensation
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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
- B01D53/005—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 by heat treatment
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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
- B01D53/14—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 by absorption
- B01D53/1456—Removing acid components
- B01D53/1468—Removing hydrogen sulfide
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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
- B01D53/14—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 by absorption
- B01D53/18—Absorbing units; Liquid distributors therefor
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/02—Preparation of sulfur; Purification
- C01B17/0253—Preparation of sulfur; Purification from non-gaseous sulfur compounds other than sulfides or materials containing such sulfides
- C01B17/0259—Preparation of sulfur; Purification from non-gaseous sulfur compounds other than sulfides or materials containing such sulfides by reduction of sulfates
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- C01B17/02—Preparation of sulfur; Purification
- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0426—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process characterised by the catalytic conversion
- C01B17/043—Catalytic converters
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- C01B17/04—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides
- C01B17/0404—Preparation of sulfur; Purification from gaseous sulfur compounds including gaseous sulfides by processes comprising a dry catalytic conversion of hydrogen sulfide-containing gases, e.g. the Claus process
- C01B17/0447—Separation of the obtained sulfur
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
- F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
- F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
- F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
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Abstract
The invention belongs to the technical field of petroleum processing, and particularly relates to a system and a process for preparing sulfur by efficiently treating alkylated waste acid. According to the system for preparing sulfur by efficiently treating the alkylated waste acid, disclosed by the invention, the treatment of the alkylated waste acid can be realized by utilizing the existing sulfur recovery device, and compared with the existing other alkylated waste acid treatment methods, a great amount of cost is saved; the waste dust adsorber filled with the de-iron scale-containing catalyst is additionally arranged to adsorb the waste dust generated by cracking the waste acid, so that the problems of catalyst poisoning and subsequent equipment blockage caused by the waste dust are prevented; and by reasonably grading the catalyst in the two-stage conversion reactor, SO in the high-temperature process gas is reasonably treated 3 The problem of corrosion of the device, which is possibly caused, is avoided, the influence of the introduction of the alkylated waste acid on the sulfur device is effectively eliminated, the requirement of the alkylated waste acid on the treatment of the sulfur device can be met, and the long-period operation of the sulfur recovery device is ensured.
Description
Technical Field
The invention belongs to the technical field of petroleum processing, and particularly relates to a system and a process for preparing sulfur by efficiently treating alkylated waste acid.
Background
The alkylation reaction is a process of reacting isobutane and olefin under the action of a strong acid catalyst to generate alkylate, the obtained alkylate is high in octane number and small in sensitivity (the difference between the research octane number and the motor octane number), does not contain sulfur, aromatic hydrocarbon and olefin, has ideal volatility and clean combustibility, is an ideal blending component of aviation gasoline and motor gasoline, and is an urgent requirement particularly along with the upgrading of the quality of gasoline, and the importance of alkylation is increasingly highlighted.
At present, the oil refineries in China mostly adopt a sulfuric acid alkylation process with concentrated sulfuric acid as a catalyst, and under the process, 80-100kg of waste sulfuric acid with the concentration of 80% -85% is generated every 1t of alkylate. In the waste sulfuric acid produced. The waste sulfuric acid is a colloidal liquid with high viscosity, and besides sulfuric acid, the waste sulfuric acid also contains 8% -14% of organic matters (polymer oil) and moisture, and has the advantages of black and red color, unstable property, emission of special odor, difficult treatment, incapability of being utilized and serious pollution to the ecological environment. Therefore, how to solve the rationalization treatment of waste acid is also a key technology for limiting the development of sulfuric acid alkylation process.
At present, the conventional sulfuric acid alkylation waste acid treatment mode mainly comprises the following steps: preparing industrial sulfuric acid, producing white carbon black or producing ammonium sulfate through high-temperature pyrolysis; the high-temperature thermal cracking method is the most commonly used waste acid treatment process of the alkylation device at home and abroad at present, but because the equipment material requirement is higher and the process flow is more complex, the investment of single-system equipment is large, the introduction of the data exists, and a waste acid combustion cracking recovery device with the treatment capacity of 1 ten thousand tons/year at least needs 1 hundred million investment, and is not suitable for actual production; the method for preparing precipitated white carbon black and petroleum antirust agent by using the alkylated waste sulfuric acid, or preparing ammonium sulfate by using the alkylated waste sulfuric acid and ammonia water, has simple process and low investment, but the oil (polymerized oil) separated in the reaction process cannot be effectively treated, and is still a pollution source.
In order to solve the problems, most refineries in China are matched with 2-3 sets of sulfur recovery devices, and recovery treatment is realized by directly introducing waste acid into the sulfur recovery devices: sulfur dioxide is generated by high-temperature decomposition of the alkylated waste acid introduced into a sulfur producer of the sulfur device, and the sulfur dioxide and hydrogen sulfide further react with claus to generate elemental sulfur under the action of a sulfur recovery catalyst of the sulfur producer, so that the recycling of sulfur resources is realized. According to the scheme, for the recovery of waste acid, the waste acid can be treated by the existing sulfur recovery unit, an independent waste acid recovery device is not required to be established, the investment is saved, and the method has great advantages; in addition, the waste acid has large treatment capacity, smaller limited conditions and no secondary pollution, meets the requirement of environmental protection technology, and also becomes the first choice waste acid recovery technology of most oil refineries at present.
However, as the alkylated waste acid contains a certain amount of organic matters and a small amount of iron, incomplete combustion of the organic matters tends to cause carbon deposition of the catalyst, and the normal operation of the sulfur recovery device is affected; moreover, the existence of iron can generate a large amount of waste dust to influence the performance of the catalyst, and can increase the iron content in the sulfur product to cause the iron content of the sulfur product to exceed the standard; in addition, a small amount of sulfur trioxide exists in the process gas after the waste acid is subjected to high-temperature pyrolysis in the sulfur recovery furnace, and if the sulfur trioxide cannot be treated in time, serious corrosion problems can be caused to sulfur device equipment in the subsequent process. For example, chinese patent CN102951614A discloses a filling method of a sulfur recovery catalyst, when the volume content of hydrocarbon gas in acid gas of a sulfur recovery device is 4-30%, the sulfur conversion rate of the sulfur recovery device is more than or equal to 96%, and the service life of the catalyst is more than or equal to 6 years; as another example, chinese patent CN102951613a discloses a catalyst grading method of an acid gas treatment sulfur recovery device, the overall service life of the graded catalyst can reach 6 years, and the flue gas emission reaches the standard; as another example, chinese patent CN101659400a discloses a catalyst combination process of a sulfur recovery device, which has high sulfur recovery rate, and the desulfurized tail gas can completely meet the national emission requirements of GB 16297-1996. The device can be used for recycling sulfur, but when the alkylated waste acid is treated by a sulfur device, the problems of exceeding the iron content of a sulfur product, coking of the catalyst and the like can occur by adopting the catalyst grading scheme, and meanwhile, the total sulfur conversion rate of the device is reduced, and the service life of the catalyst is shortened.
In order to solve the above problems, chinese patent CN106256760a discloses a process for treating alkylated waste acid by using a sulfur device, which realizes low investment and high efficiency treatment of alkylated waste acid; reasonable treatment of SO in high-temperature process gas 3 Avoiding the corrosion problem of the device caused by SO 3 The conversion rate reaches more than 97%; meanwhile, the influence of residual iron in the waste acid can be eliminated, and the mass content of iron in the sulfur product is less than 0.005%; the influence of carbon deposit on the catalyst is eliminated, and the Claus catalyst is effectively protected. The catalyst can keep high Claus catalytic activity, organic sulfur hydrolysis activity, and the total sulfur conversion rate of the device reaches more than 96.5%. However, as process requirements continue to increase, the process still has the following problems:
first, the device cannot meet the flue gas SO 2 Emission standards are reaching standards, with the increasing deterioration of environment, environmental regulations in China are becoming stricter, and new environmental standards (GB 31570-2015) are issued by China in 2015, wherein: flue gas SO of sulfur device 2 The emission concentration limit is generally required to reach 400mg/Nm in regions 3 In the following, the requirements in the important areas reach 100mg/Nm 3 The following are set forth; and sulfur tail gas SO 2 The emission is also one of important indexes in checking and accounting the total pollutant amount of the environmental protection department, the new sulfur device is executed after 2015 is 7 months and 1 day, and the old sulfur device is executed after 2017 is 7 months and 1 day. First stage in the process deviceThe upper part of the converter is filled with 5-30% of iron-removing scale-holding protective agent, which is equivalent to 5-30% of the reduction of the amount of the Claus catalyst in the whole device, and can reduce a part of conversion rate of the device, especially organic sulfur conversion rate, thereby causing flue gas SO of the device 2 Cannot meet the requirements of the latest environmental protection regulations;
secondly, the limited scale capacity of the iron and scale removal catalyst in the device can influence the long-period operation of the device, and although the scale capacity of the iron and scale removal catalyst filled in the process can reach 30 percent, the alkylation device commonly has serious corrosion problem, and can cause higher impurity content in waste acid, and according to the knowledge, under the normal operation condition of the 3.5 ten thousand ton/year waste acid cracking device, 1kg of waste dust (the main component is ferric sulfate) is generated per hour; therefore, once the alkylation device fluctuates, when the impurity content in the waste acid is too high, the iron removal scale containing catalyst is easy to lose efficacy, so that the normal operation of the catalyst of the sulfur recovery device is affected, and when serious, the catalyst of the sulfur recovery device is also caused to stop in an unplanned way;
Furthermore, the de-iron scale-containing catalyst is filled in the reactor of the device and cannot be treated independently, once the de-iron scale-containing catalyst is in a problem in the use process in the process, the whole device is stopped to treat the problem, and great operation hidden danger exists.
Therefore, in order to realize the recovery treatment of the alkylated waste acid introduced into the sulfur device and ensure the long-period stable operation of the device, the device and the process are necessary to be further perfected, and further a treatment device and a process for efficiently treating the alkylated waste acid are developed, so that the method has positive significance.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a recovery device for preparing sulfur by using the alkylation waste acid, SO as to eliminate the influence on the normal operation of the device after the alkylation waste acid is introduced into the sulfur device, eliminate the influence on the catalyst of the sulfur recovery device, the quality of sulfur products, equipment and the like caused by the treatment of the alkylation waste acid in the sulfur recovery device, and solve the problem that the alkylation waste acid is introduced into the flue gas SO of the sulfur device 2 The practical problem that the emission does not reach the standard ensures the long-period normal operation of the sulfur recovery device, and solves the problemsSolving the practical problem that the waste acid of the existing and newly-built alkylation devices is difficult to treat;
The second technical problem to be solved by the invention is to provide a recovery process for preparing sulfur by using the alkylated waste acid, which can meet the treatment requirement of the alkylated waste acid in a sulfur device, eliminate the influence of the introduction of the alkylated waste acid on the sulfur device, realize the standard emission of the device and ensure the long-period operation of the sulfur recovery device.
In order to solve the technical problems, the system for preparing sulfur by efficiently treating alkylated waste acid comprises a thermal reaction unit, a catalytic reaction unit and a tail gas purifying unit which are sequentially connected; wherein,
the thermal reaction unit includes:
sulfur production furnace, alkylated waste acid to be treated and H-containing waste acid 2 S, acid gas reacts in the sulfur producing furnace to generate process gas containing elemental sulfur;
the waste dust absorber is filled with an iron-removing scale-containing catalyst and is used for absorbing iron-containing waste dust in process gas;
the sulfur cooler is used for condensing the process gas after adsorption treatment, collecting condensed liquid sulfur and enabling the rest process gas to enter the catalytic reaction unit;
the catalytic reaction unit includes:
the primary converter is filled with an oxygen leakage removal catalyst, an organic sulfur hydrolysis catalyst and a hydrogenation catalyst, and the process gas can simultaneously perform a Claus reaction, an organic sulfur hydrolysis reaction and an SO 3 Carrying out reduction reaction to obtain elemental sulfur and catalytic tail gas;
the secondary converter is internally provided with a sulfur recovery catalyst, and the catalytic tail gas is subjected to Claus catalytic conversion to obtain elemental sulfur and Claus tail gas;
the purifying exhaust gas unit includes:
a hydrogenation reactor, wherein the Claus tail gas is used for the hydrogenation conversion of sulfur-containing compounds into H 2 S, obtain H-containing 2 S, hydrogenation tail gas;
an absorption tower for absorbing H in the hydrogenated tail gas 2 S, obtaining purified tail gas;
and the tail gas incinerator is used for incinerating and discharging the purified tail gas.
The waste dust adsorber is internally filled with the de-iron scale-holding catalyst, so that impurities such as waste dust generated by cracking waste acid in process gas can be removed, the catalyst in the second-stage converter of the catalytic reaction unit is protected, and downstream equipment is prevented from being blocked. Preferably, the two waste dust adsorbers are arranged, one is on and the other is off, so that waste dust generated by cracking waste acid can be prevented from causing catalyst poisoning and subsequent equipment blockage. The rising pressure drop of the waste dust adsorber indicates that the scale capacity of the iron removal scale containing catalyst in the device is close to saturation, and at the moment, the spare adsorber needs to be replaced in time, and meanwhile, the catalyst of the adsorber is replaced. The operating temperature of the waste dust adsorber is 280-350 ℃. The scale capacity of the de-iron scale-tolerant catalyst is more than 30%.
Specifically, in the waste dust adsorber:
the iron-removing scale-holding catalyst can be any feasible iron-removing catalyst with an iron-removing function in the prior art, the specific filling amount is determined according to the scale of the device, the waste dust amount is free from fixing requirements, the size is changeable, the replacement frequency is small, and the replacement is not needed frequently.
Specifically, a waste heat boiler is further arranged between the sulfur producing furnace and the waste dust adsorber and is used for recovering part of heat.
Specifically, in the primary converter, the oxygen leakage removal catalyst is filled in the top position, the organic sulfur hydrolysis catalyst is filled in the middle position, and the hydrogenation catalyst is filled in the bottom position.
wherein ,
the oxygen-removing catalyst is any Claus sulfur recovery catalyst with an oxygen-removing function;
the organosulfur hydrolysis catalyst may be any claus sulfur recovery catalyst having a relatively high organosulfur hydrolysis rate;
the hydrogenation catalyst can be any low-temperature type tail gas hydrogenation catalyst;
the sulfur recovery catalyst may be any sulfur recovery catalyst having a relatively high activity.
In particular, small amounts of SO are produced due to the cracking of the alkylated spent acid in the sulfur producer 3 ，SO 3 The corrosion is strong, and the subsequent equipment is corroded; in addition, the conversion rate of Claus in the sulfur producing furnace is reduced when the alkylated waste acid is introduced into the sulfur producing device, and part of organic sulfur is generated in the cracking process of the organic polymer contained in the waste acid, SO that the catalyst filling in the primary converter and the secondary converter is preferably carried out according to a certain grading scheme, and on one hand, SO generated by the cracking of the waste acid is ensured 3 Reduction to SO 2 On the other hand, the normal operation of the Claus and organic sulfur reactions of the sulfur device is ensured, and the standard emission of the flue gas of the device is ensured so as to ensure the normal operation of the device.
Specifically, in the primary converter, the upper part is filled with a catalyst for oxygen leakage removal with the height of 20-40%, the middle part is filled with a catalyst for organic sulfur hydrolysis with the height of 45-75%, and the lower part is filled with a catalyst for low-temperature high-activity hydrogenation with the height of 5-15%. This is mainly because: the oxygen leakage catalyst is filled at the upper part of the primary converter, so that oxygen leakage in the process gas can be removed, the catalyst is protected from being sulfated, the air distribution quantity of the sulfur production furnace is required to be increased to ensure complete cracking of the alkylated waste acid after the alkylated waste acid is introduced into the sulfur recovery device for treatment, oxygen leakage is likely to exist, the oxygen leakage catalyst can be used for effectively protecting the catalyst, and the reaction activity is prevented from being reduced due to sulfation of the catalyst; the organic sulfur hydrolysis catalyst is filled in the middle of the primary converter, so that the hydrolysis rate of organic sulfur in the process gas can be effectively improved, and the influence of more organic sulfur generated by organic polymers in the alkylated waste acid on the normal operation of a sulfur device is eliminated; the lower part of the primary converter is filled with a high-temperature high-activity hydrogenation catalyst, SO that waste acid can be cracked to produce SO (sulfur dioxide) 3 Reduction to SO 2 SO elimination 3 Corrosion to subsequent equipment.
The secondary converter is filled with alumina-based sulfur recovery catalyst with large specific surface area, so that the Claus conversion rate can be effectively improved, and the influence of waste acid introduction on the Claus conversion rate of the device is eliminated.
Preferably, the hydrogenation reactor is fully filled with the high-activity hydrogenation catalyst, so that H in the Claus tail gas can be removed 2 Sulfur-containing compounds other than S are sufficiently hydrogenated or hydrolyzed to ensure higher sulfur recovery from the plant.
Specifically, a sulfur cooler is arranged behind the first converter and the second converter respectively.
Specifically, a primary converter reheater and a secondary converter reheater are further arranged in front of the first converter and the second converter respectively.
The invention also discloses a process for preparing sulfur by efficiently treating alkylated waste acid based on the system, which comprises the following steps:
(1) Will contain H 2 S acid gas and alkylated waste acid to be treated are introduced into the sulfur producing furnace, and the sulfur producing furnace contains H 2 S acid gas is combusted and converted into SO in the sulfur producing furnace 2 The alkylated waste acid is subjected to high-temperature pyrolysis to generate SO 2 And a small amount of SO 3 The method comprises the steps of carrying out a first treatment on the surface of the The H obtained 2 S and SO 2 Claus reaction occurs to produce a process gas containing elemental sulfur; inputting the process gas into the waste dust adsorber, and removing waste dust in the process gas through catalysis; the process gas after adsorption treatment enters the sulfur cooler to be condensed to obtain liquid sulfur and is collected, and the process gas continuously enters the catalytic reaction unit;
(2) The process gas enters the first converter and is subjected to the Claus reaction, the organic sulfur hydrolysis reaction and the SO simultaneously under the action of a selected catalyst 3 Carrying out reduction reaction to obtain elemental sulfur and catalytic tail gas; collecting elemental sulfur and continuously feeding the obtained catalytic tail gas into the second converter, and carrying out Claus catalytic conversion under the action of a selected catalyst to obtain elemental sulfur and Claus tail gas, wherein the Claus tail gas enters the tail gas purification unit;
(3) The Claus tail gas is subjected to hydrogenation catalytic reaction in the hydrogenation reactor to convert sulfur-containing compounds in the Claus tail gas into H 2 S, entering an absorption tower to absorb H 2 S, S; the purified tail gas is introduced into the tail gas incinerator to be incinerated and then discharged.
Specifically, in the step (1), the method further comprises the step of introducing natural gas into the sulfur producing furnace as a combustion accompanying gas.
Specifically, the step (2) further includes a step of condensing the obtained elemental sulfur and tail gas in a sulfur cooler after the catalytic reaction of the primary converter and the secondary converter, and collecting liquid sulfur.
Specifically, the method further comprises the step of heating the corresponding process gas before entering the primary converter, the secondary converter and the hydrogenation reactor.
According to the system for preparing sulfur by efficiently treating the alkylated waste acid, disclosed by the invention, the treatment of the alkylated waste acid can be realized by utilizing the existing sulfur recovery device, and compared with the existing other alkylated waste acid treatment methods, a great amount of cost is saved; the system comprises a thermal reaction unit, a catalytic reaction unit and a tail gas purifying unit, and the waste dust generated by cracking waste acid is adsorbed and discharged by additionally arranging a waste dust adsorber filled with a de-iron scale-holding catalyst so as to prevent the problems of catalyst poisoning and subsequent equipment blockage caused by the waste dust; and by reasonably grading the catalyst in the two-stage conversion reactor, SO in the high-temperature process gas is reasonably treated 3 The problem of corrosion of the device, which is possibly caused, is avoided, the influence of the introduction of the alkylated waste acid on the sulfur device is effectively eliminated, the requirement of the alkylated waste acid on the treatment of the sulfur device can be met, and the long-period operation of the sulfur recovery device is ensured. The system can realize that the iron content in the sulfur product is less than 0.005%; the total sulfur conversion rate of the device reaches more than 97.0 percent; flue gas SO of device 2 The discharge is less than 100mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The service life of the catalyst is more than or equal to 6 years, and the long-period operation of the sulfur recovery device can be realized.
In the system of the invention, the upper part of the primary converter is filled with 20-40% of oxygen-removing catalyst, the middle part is filled with 45-75% of organic sulfur hydrolysis catalyst, and the lower part is filled with 5-15% of low-temperature high-activity hydrogenation catalystThe method comprises the steps of carrying out a first treatment on the surface of the The secondary converter is fully filled with alumina-based sulfur recovery catalyst with large specific surface area; the tail gas hydrogenation converter is fully filled with high-temperature high-activity hydrogenation catalyst. On the one hand ensure SO generated by cracking waste acid 3 Reduction to SO 2 On the other hand, the normal operation of the Claus and organic sulfur reactions of the sulfur device is ensured, and the standard discharge of the flue gas of the device is ensured. Through detection, SO in the whole catalytic conversion reaction 3 The conversion rate reaches more than 97%; effectively improves the sulfur recovery efficiency of the device and SO (sulfur oxide) in the flue gas of the device 2 The discharge is less than 100mg/m 3 The influence of waste acid introduction on the operation of the device is eliminated.
Drawings
In order that the invention may be more readily understood, a more particular description of the invention will be rendered by reference to specific embodiments thereof which are illustrated in the appended drawings, in which,
FIG. 1 is a schematic diagram of a system according to the present invention;
FIG. 2 is a schematic illustration of the loading of catalyst in a primary converter according to the present invention;
FIG. 3 is a schematic illustration of the loading of catalyst in a secondary converter according to the present invention;
FIG. 4 is a flow chart of the treatment process in comparative example 1;
the reference numerals in the drawings are as follows: the device comprises a 1-sulfur making furnace, a 2-waste heat boiler, a 3-waste dust absorber, a 4-primary sulfur cooler, a 5-primary converter reheater, a 6-primary converter, a 7-secondary sulfur cooler, an 8-secondary converter reheater, a 9-secondary converter, a 10-tertiary sulfur cooler, an 11-tail gas reheater, a 12-hydrogenation reactor, a 13-hydrogenation tail gas heat exchanger, a 14-quenching tower, a 15-absorption tower, a 16-liquid sulfur pool, a 17-tail gas incinerator and an 18-chimney.
Detailed Description
The system for preparing sulfur by efficiently treating alkylated waste acid comprises a thermal reaction unit, a catalytic reaction unit and a tail gas purifying unit which are sequentially connected, wherein the structural schematic diagram is shown in fig. 1; wherein,
the thermal reaction unit includes:
sulfur production furnace 1, alkylated waste acid to be treated and H-containing 2 S, acid gas reacts in the sulfur producing furnace 1 to generate process gas containing elemental sulfur;
a waste heat boiler 2, the generated process gas recovering part of heat through the waste heat boiler 2;
A waste dust absorber 3, wherein an iron-removing scale-containing catalyst is filled in the waste dust absorber 3, and iron-containing waste dust generated by the impurities in the alkylated waste acid is captured in a catalyst pore canal and used for the iron-containing waste dust in the process gas;
the primary sulfur cooler 4 is used for condensing the process gas after adsorption and filtration treatment in the primary sulfur cooler 4, collecting liquid sulfur obtained by condensation in the liquid sulfur tank 16, and enabling the process gas to enter the catalytic reaction unit for subsequent reaction;
the catalytic reaction unit includes:
a primary converter reheater 5, wherein the process gas entering the catalytic reaction unit is heated in the primary converter reheater 5;
the primary converter 6 is filled with an oxygen leakage removal catalyst, an organic sulfur hydrolysis catalyst and a low-temperature high-activity hydrogenation catalyst; the process gas entering the primary converter 6 can be subjected to the claus reaction, the organosulfur hydrolysis reaction and the SO simultaneously 3 The reduction reaction is carried out to obtain elemental sulfur and catalytic tail gas respectively; as shown in the catalyst filling schematic diagram in fig. 2, the upper part of the primary converter 6 is filled with 20-40% of high oxygen leakage catalyst, the middle part is filled with 45-75% of high organic sulfur hydrolysis catalyst, and the lower part is filled with 5-15% of high low-temperature high-activity hydrogenation catalyst;
The secondary sulfur cooler 7 is used for condensing elemental sulfur and catalytic tail gas after catalytic reaction by the primary converter 6 in the secondary sulfur cooler 7, the obtained liquid sulfur is collected and enters the liquid sulfur pool 16, and the condensed catalytic tail gas is continuously reacted;
a secondary converter reheater 8, wherein the catalytic tail gas is heated in the secondary converter reheater 8;
a second-stage converter 9, as shown in a catalyst filling schematic diagram in fig. 3, wherein the second-stage converter 9 is filled with alumina-based sulfur recovery catalyst with large specific surface area, and the catalytic tail gas is subjected to Claus catalytic conversion to obtain elemental sulfur and Claus tail gas;
the tertiary sulfur cooler 10 is used for condensing elemental sulfur and Claus tail gas after catalytic reaction by the secondary converter 9, the obtained liquid sulfur is collected and enters the liquid sulfur pool 16, and the condensed Claus tail gas continuously enters a subsequent tail gas purifying unit;
the purifying exhaust gas unit includes:
a tail gas reheater 11, wherein the separated Claus tail gas enters the tail gas reheater 11 for heating treatment;
a hydrogenation reactor 12, wherein the hydrogenation reactor 12 is fully filled with a high-activity hydrogenation catalyst, and the heated Claus tail gas is used for hydrogenation conversion of sulfur-containing compounds into H in the hydrogenation reactor 12 2 S, can ensure H removal in the Claus tail gas 2 Fully hydrogenating or hydrolyzing sulfur-containing compounds except S to obtain H-containing compounds 2 S, hydrogenation tail gas;
hydrogenation tail gas heat exchanger 13, H-containing after reaction 2 S, carrying out heat exchange treatment on hydrogenation tail gas through the hydrogenation tail gas heat exchanger 13;
quench tower 14, said H-containing 2 S, the hydrogenated tail gas enters the quenching tower 14 for cooling treatment;
an absorption tower 15, wherein an amine liquid is arranged in the absorption tower 15 and is used for absorbing H in the hydrogenation tail gas 2 S, further obtaining purified tail gas;
a liquid sulfur tank 16 for absorbing liquid sulfur obtained by condensing each of the sulfur coolers;
the tail gas incinerator 17 incinerates the tail gas purified by the absorber 15 and discharges the tail gas through the chimney 18.
Based on the system shown in the attached figure 1, the process for preparing sulfur by efficiently treating alkylated waste acid comprises the following steps:
(1) The thermal reaction unit is as follows: containing H 2 Partial combustion of S acid gas into SO in sulfur producing furnace 2 The alkylation waste acid to be treated is subjected to high-temperature pyrolysis in the sulfur producing furnace 1 to generate SO 2 And a small amount of SO 3 Because the sulfur producing furnace mixes and burns the acid gas, the waste acid and the air in the sulfur producing furnace, in order to ensure the normal reaction of the acid gas and the complete cracking of the alkylated waste acid, partial natural gas is introduced into the sulfur producing furnace as the accompanying gas, the burning temperature is controlled between 950 and 1400 ℃ and the burning temperature is controlled between partial H 2 Conversion of S combustion to SO 2 Cracking waste acid at high temperature to generate SO 2 ，H 2S and SO2 Claus reaction takes place at high temperature to produce a process gas containing elemental sulphur (containing elemental sulphur, H) 2 S、SO 2 、SO 3 And COS, CS 2 And part of waste dust), the process gas enters the waste dust absorber 3 after part of heat is recovered by the waste heat boiler 2, and the waste dust in the process gas is removed under the action of a catalyst in the waste dust absorber 3; the process gas at the outlet of the waste dust adsorber 3 enters the primary sulfur cooler 4 for condensation, liquid sulfur obtained by condensation is separated from the process gas and then enters the liquid sulfur tank 16, and the separated process gas enters a subsequent catalytic reaction unit;
the thermal reaction unit involves a reaction process comprising:
2H 2 S+3O 2 →2SO 2 +2H 2 O (1)
2H 2 SO 4 →2SO 2 +2H 2 O+O 2 (2)
SO 2 +2H 2 S→2H 2 O+3S (3)
(2) The catalytic reaction unit is as follows: the separated process gas enters the primary converter 6 after being heated by the primary converter reheater 5, reacts under the action of the catalyst with selected grading, and simultaneously carries out the Claus reaction, the organic sulfur hydrolysis reaction and the SO 3 Reduction reaction, claus reaction of hydrogen sulfide and sulfur dioxide to generate elemental sulfur, hydrolysis reaction of organic sulfur to generate hydrogen sulfide, SO 3 Reduction reaction takes place to generate SO 2 The reacted catalytic tail gas enters the secondary sulfur cooler 7 to be condensed, elemental sulfur in the catalytic tail gas enters the liquid sulfur tank 16 to obtain liquid sulfur, the condensed catalytic tail gas is heated by the secondary converter reheater 8 and then continuously enters the secondary converter 9 to react, and the catalytic tail gas is subjected to Claus catalytic conversion under the action of a catalyst to be generated Elemental sulfur and Claus tail gas; the elemental sulfur and the Claus tail gas enter the three-stage sulfur cooler to be condensed, the liquid sulfur generated after the condensation also enters the liquid sulfur tank 16, and the Claus tail gas after the condensation (containing trace elements of sulfur and H 2 S、SO 2 And COS, CS 2 Sulfide) enters a subsequent tail gas purifying unit;
the reaction process involved in the catalytic reaction unit comprises the following steps:
SO 2 +2H 2 S→2H 2 O+3S (4)
COS+H 2 O→H 2 S+CO 2 (5)
CS 2 +2H 2 O→2H 2 S+CO 2 (6)
SO 3 +CO→SO 2 +CO 2 (7)
(3) The tail gas purifying unit is as follows: after being heated to 200-300 ℃ by a tail gas reheater 11, the condensed Claus tail gas enters a hydrogenation reactor 12, and elemental sulfur and SO carried in the tail gas are reacted under the action of a hydrogenation catalyst 2 All hydrogenation is converted into H 2 S，COS、CS 2 Hydrolysis to H 2 S, S; then enters an absorption tower 15 containing amine liquid after heat exchange by a hydrogenation tail gas heat exchanger 12 and cooling by a quenching tower 13, and the amine liquid absorbs H in the hydrogenation tail gas 2 S, S; the obtained purified tail gas can be introduced into a liquid sulfur tank 16 as stripping gas for liquid sulfur degassing to bubble and degas the liquid sulfur, and remove trace H dissolved in the liquid sulfur 2 S and contains H 2 S and the waste gas of the sulfur vapor, which is degassed by liquid sulfur, are pumped out by a steam injector, are mixed with the Claus tail gas and then enter the hydrogenation reactor 12 for treatment, and the rest of the purified tail gas is introduced into the incinerator 17 and is discharged by the chimney 18 after being incinerated, so that the new environmental protection standard requirement is met.
The following examples of the invention are provided:
the iron-removing scale-tolerant catalyst is preferably a LH-04 catalyst. The LH-04 catalytic protecting agent is a catalytic protecting agent with the functions of removing iron and scale and protecting main catalyst, which is developed by the institute of China and petrochemical company, qilu company. The LH-04 catalyst is honeycomb-shaped, has a proper pore canal structure, has the capability of removing large impurity particles, can deposit metal elements into own pore canal, has good coking resistance and iron removal performance, has higher activity, and has the iron removal capacity of more than 30 percent;
the oxygen-removing catalyst is preferably LS-971 catalyst developed by the institute of petrochemical Oldham company. LS-971 catalyst is a high Claus activity and de-O-leak 2 The protective type double-function sulfur recovery catalyst is suitable for Claus sulfur recovery devices in the fields of petrochemical industry, coal chemical industry and the like, can be used for the whole bed layer of a Claus reactor of any stage of the sulfur recovery device or can be used for layered filling with other catalysts with different functions or types, and a large amount of reaction heat can be generated in the process of removing oxygen leakage, so that the reaction temperature is increased, and the hydrolysis reaction of organic sulfur is facilitated at high temperature. Under the same device and the same process condition, the total sulfur conversion rate can be improved by about 1 to 1.7 percent, and is especially suitable for acid gas H 2 The sulfur recovery device with larger S content or flow variation amplitude is used;
the organic sulfur hydrolysis catalyst is preferably LS-981G catalyst developed by the institute of petrochemical Oldham's company. LS-981G catalyst is a TiO 2 The catalyst for recovering the base sulfur has excellent organic sulfur hydrolysis activity. Hydrolysis reaction of the catalyst on organic sulfide and H 2 S and SO 2 Has higher catalytic activity and almost reaches thermodynamic equilibrium; for "O 2 Poisoning insensitivity, hydrolysis reaction resistance O 2 "poisoning ability of 0.2% (v), up to 1% (v) in the case of the Claus reaction, and once high concentrations of O are excluded 2 The activity is almost completely restored; for the same conversion level, a shorter contact time of about 3 seconds is allowed, corresponding to 1000 hours -1 -1200h -1 Space velocity, and thus reactor volume, can be reduced;
the specific surface area of the alumina-based sulfur recovery catalyst with large specific surface area is higher than 350m 2 Preferably LS-02 catalyst developed by the institute of Mitsubishi Oldham corporation. LS-02 catalyst is a new one with larger specific surface area and higher pore volume developed based on LS-300The catalytic Claus has high activity, strong heat aging resistance and hydrothermal aging resistance, uniform particles, small abrasion and high crushing strength, thereby ensuring the long-period operation of the catalyst; the catalyst has more reasonable pore structure and more macropores, and the pore structure is in bimodal distribution, so that sulfur generated by the reaction rapidly leaves the pore canal of the catalyst, and the Claus activity and the organic sulfur hydrolysis activity of the catalyst are further improved.
The low-temperature oxygen-resistant high-activity hydrogenation catalyst is preferably an LSH-03A catalyst developed by the institute of Oldham's GmbH, the inlet temperature of the hydrogenation reactor can be controlled to 220-260 ℃, the activity of the catalyst is improved by more than 30% compared with that of a common catalyst, the catalyst has excellent low-temperature hydrogenation and hydrolysis activities, and the content of organic sulfur in hydrogenated tail gas can be ensured to be lower than 20ppm.
The catalyst of the invention can be purchased from market, and the physicochemical properties and technical indexes are shown in the following table 1.
TABLE 1 catalyst physicochemical Properties and technical indicators
Example 1
The process flow of the embodiment is shown in fig. 1, and the process of the embodiment is applied to a sulfur recovery device, and the device is a 40kt/a sulfur recovery device.
H 2 The acid gas with the S content of 65% is subjected to combustion reaction in the sulfur making furnace 1, the alkylated waste acid with the sulfuric acid content of 85% and the organic matter content of 15% is introduced into the sulfur making furnace to generate high-temperature cracking reaction, and natural gas is introduced as the accompanying gas to control the temperature of the sulfur making furnace to 1050 ℃ in order to ensure the normal reaction of the acid gas and the complete cracking of the waste acid. The process gas at the outlet of the sulfur producing furnace 1 enters a waste dust adsorber 3 (the operation temperature is 335 ℃ and is filled with LH-04 catalyst protecting agent) after part of heat is recovered by a waste heat boiler 2, and waste dust (the main component is ferric sulfate) in the waste dust is deposited in a catalyst inner pore canal; the process gas for absorbing and removing the waste dust is cooled by a primary sulfur cooler 4 to recover elemental sulfur and then reheated by a primary converter reheater 5 Then enters a first-stage converter 6 (the catalyst grading scheme is that an upper part is filled with LS-971 oxygen-removing catalyst with the height of 35 percent, a middle part is filled with LS-981G organic sulfur hydrolysis catalyst with the height of 55 percent, and a lower part is filled with LSH-03A high-activity hydrogenation catalyst with the height of 10 percent), H in the process gas is in the first-stage converter 6 2S and SO2 Claus reaction is carried out to recycle sulfur resources, organic sulfur in the process gas is hydrolyzed to generate hydrogen sulfide, and SO in the process gas 3 Is reduced to SO 2 The method comprises the steps of carrying out a first treatment on the surface of the The process gas at the outlet of the primary converter 6 is recycled to generate elemental sulfur through a secondary sulfur cooler 7, and enters a secondary converter 9 (catalyst grading scheme: fully filled with LS-02 alumina-based sulfur recycling catalyst with large specific surface area) after being reheated by a secondary converter reheater 8, claus reaction is continuously carried out, and sulfur resources are further recycled; the process gas at the outlet of the secondary converter 9 is subjected to recovery of elemental sulfur by the tertiary sulfur cooler 10 to obtain Claus tail gas; the Claus tail gas is reheated to 230 ℃ by a hydrogenation tail gas reheater 11 and then enters a hydrogenation reactor 12, and sulfur-containing compounds are converted into H through hydrogenation under the action of a hydrogenation internal catalyst (LSH-03A) in the hydrogenation reactor 12 2 S, the generated hydrogenation tail gas is subjected to heat exchange condensation through a hydrogenation tail gas heat exchanger 13 and then enters a quenching tower 14 for cooling, the cooled hydrogenation tail gas enters an amine liquid absorption tower 15, and H in the hydrogenation tail gas is absorbed by amine liquid 2 S, generating purified tail gas; introducing part of the purified tail gas into a liquid sulfur pool 16 as gas stripping gas for liquid sulfur degassing, and introducing the gas stripping gas into a hydrogenation reactor 12 for treatment after the gas stripping gas for liquid sulfur degassing is extracted; the rest of purified tail gas is introduced into an incinerator 17 for incineration and then is discharged through a chimney 18.
The total sulfur conversion rate in the embodiment is 97.11%, and the flue gas SO is detected 2 60mg/m 3 The iron content of the sulfur product was 0.0010% (m/m); the service life of the catalyst is more than 6 years.
Example 2
The process flow of the embodiment is shown in fig. 1, and the process of the embodiment is applied to a sulfur recovery device, and the device is an 80kt/a sulfur recovery device.
H 2 The acid gas with S content of 72 percent is burnt in the sulfur producing furnace 1, the sulfuric acid content is 90 percent, and the organic matter is 10 percentThe alkylated waste acid is introduced into a sulfur producing furnace to generate high-temperature cracking reaction, natural gas is introduced as a combustion accompanying gas for ensuring the normal reaction of the acid gas and the complete cracking of the waste acid, and the temperature of the sulfur producing furnace is controlled to be 1220 ℃. The process gas at the outlet of the sulfur producing furnace 1 enters a waste dust adsorber 3 (the operation temperature is 380 ℃ C.) after part of heat is recovered by a waste heat boiler 2, LH-04 catalytic protection agent is filled in the waste dust adsorber, and waste dust (the main component is ferric sulfate) in the waste dust adsorber is deposited in a catalyst inner pore channel; the process gas for absorbing and removing waste dust is cooled by a primary sulfur cooler 4 to recover elemental sulfur, and then is reheated by a primary converter reheater 5 to enter a primary converter 6 (the catalyst grading scheme is that 40 percent of LS-971 oxygen-removing catalyst is filled in the upper part, 45 percent of LS-981G organic sulfur hydrolysis catalyst is filled in the middle part, 15 percent of LSH-03A low-temperature high-activity hydrogenation catalyst is filled in the lower part), and H in the process gas is in the primary converter 6 2S and SO2 Claus reaction is carried out to recycle sulfur resources, organic sulfur in the process gas is hydrolyzed to generate hydrogen sulfide, and SO in the process gas 3 Is reduced to SO 2 The method comprises the steps of carrying out a first treatment on the surface of the The process gas at the outlet of the primary converter 6 is recycled to generate elemental sulfur through a secondary sulfur cooler 7, and enters a secondary converter 9 (catalyst grading scheme: fully filled with LS-02 alumina-based sulfur recycling catalyst with large specific surface area) after being reheated by a secondary converter reheater 8, claus reaction is continuously carried out, and sulfur resources are further recycled; the process gas at the outlet of the secondary converter 9 is subjected to recovery of elemental sulfur by the tertiary sulfur cooler 10 to obtain Claus tail gas; the Claus tail gas is reheated to 200 ℃ by a hydrogenation tail gas reheater 11 and then enters a hydrogenation reactor 12, and sulfur-containing compounds are converted into H through hydrogenation under the action of a hydrogenation internal catalyst (LSH-03A) in the hydrogenation reactor 12 2 S, the generated hydrogenation tail gas is subjected to heat exchange condensation through a hydrogenation tail gas heat exchanger 13 and then enters a quenching tower 14 for cooling, the cooled hydrogenation tail gas enters an amine liquid absorption tower 15, and H in the hydrogenation tail gas is absorbed by amine liquid 2 S, generating purified tail gas; introducing part of the purified tail gas into a liquid sulfur pool 16 as gas stripping gas for liquid sulfur degassing, and introducing the gas stripping gas into a hydrogenation reactor 12 for treatment after the gas stripping gas for liquid sulfur degassing is extracted; the rest of purified tail gas is introduced into an incinerator 17 for incineration and then is discharged through a chimney 18.
The device in this example was tested for total sulfur conversionThe rate is 97.22%; flue gas SO 2 45mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The iron content of the sulphur product was 0.0016% (m/m); the service life of the catalyst is more than 6 years.
Example 3
The process flow of the embodiment is shown in fig. 1, and the process of the embodiment is applied to a sulfur recovery device, wherein the sulfur recovery device is 100kt/a sulfur recovery device.
H 2 The method comprises the steps that (1) an acid gas with the S content of 75% is subjected to combustion reaction in a sulfur making furnace 1, and after alkylation waste acid with the sulfuric acid content of 89% and the organic matter content of 11% is introduced into the sulfur making furnace, a high-temperature cracking reaction is carried out, so that the normal reaction of the acid gas and the complete cracking of the waste acid are ensured, natural gas is introduced as a combustion accompanying gas, and the temperature of the sulfur making furnace is controlled to be 1350 ℃. The process gas at the outlet of the sulfur producing furnace 1 enters a waste dust adsorber 3 (the operation temperature is 280 ℃ C.) after part of heat is recovered by a waste heat boiler 2, LH-04 catalytic protection agent is filled in the waste dust adsorber, and waste dust (the main component is ferric sulfate) in the waste dust adsorber is deposited in a catalyst inner pore channel; the process gas for absorbing and removing waste dust is cooled by a primary sulfur cooler 4, is reheated by a primary converter reheater 5 and enters a primary converter 6 (the catalyst grading scheme is that an upper part is filled with LS-971 oxygen-removing catalyst with 20 percent of height, a middle part is filled with LS-981G organic sulfur hydrolysis catalyst with 75 percent of height, a lower part is filled with LSH-03A low-temperature high-activity hydrogenation catalyst with 5 percent of height), and H in the process gas enters the primary converter 6 2S and SO2 Claus reaction is carried out to recycle sulfur resources, organic sulfur in the process gas is hydrolyzed to generate hydrogen sulfide, and SO in the process gas 3 Is reduced to SO 2 The method comprises the steps of carrying out a first treatment on the surface of the The process gas at the outlet of the primary converter 6 is recycled to generate elemental sulfur through a secondary sulfur cooler 7, and enters a secondary converter 9 (catalyst grading scheme: fully filled with LS-02 alumina-based sulfur recycling catalyst with large specific surface area) after being reheated by a secondary converter reheater 8, claus reaction is continuously carried out, and sulfur resources are further recycled; the process gas at the outlet of the secondary converter 9 is subjected to recovery of elemental sulfur by the tertiary sulfur cooler 10 to obtain Claus tail gas; the Claus tail gas is reheated to 280 ℃ by a hydrogenation tail gas reheater 11 and then enters a hydrogenation reactor 12, and under the action of a hydrogenation internal catalyst (LSH-03A) in the hydrogenation reactor 12, sulfur-containing compounds are addedConversion of hydrogen to H 2 S, the generated hydrogenation tail gas is subjected to heat exchange condensation through a hydrogenation tail gas heat exchanger 13 and then enters a quenching tower 14 for cooling, the cooled hydrogenation tail gas enters an amine liquid absorption tower 15, and H in the hydrogenation tail gas is absorbed by amine liquid 2 S, generating purified tail gas; introducing part of the purified tail gas into a liquid sulfur pool 16 as gas stripping gas for liquid sulfur degassing, and introducing the gas stripping gas into a hydrogenation reactor 12 for treatment after the gas stripping gas for liquid sulfur degassing is extracted; the rest of purified tail gas is introduced into an incinerator 17 for incineration and then is discharged through a chimney 18.
The total sulfur conversion in this example was examined to be 97.18%; flue gas SO 2 52mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The iron content in the sulphur product was 0.0018% (m/m); the service life of the catalyst is more than 6 years.
Example 4
The process flow of the embodiment is shown in fig. 1, and the process of the embodiment is applied to a sulfur recovery device, wherein the sulfur recovery device is 70kt/a sulfur recovery device.
H 2 The method comprises the steps that (1) an acid gas with the S content of 82% is subjected to combustion reaction in a sulfur making furnace 1, an alkylated waste acid with the sulfuric acid content of 90% and the organic matter content of 10% is introduced into the sulfur making furnace to undergo high-temperature cracking reaction, and natural gas is introduced as a combustion accompanying gas to ensure the normal reaction of the acid gas and the complete cracking of the waste acid, so that the temperature of the sulfur making furnace is controlled to be 1400 ℃. The process gas at the outlet of the sulfur producing furnace 1 enters a waste dust adsorber 3 (the operation temperature is 350 ℃ and is filled with LH-04 catalyst protecting agent) after part of heat is recovered by a waste heat boiler 2, and waste dust (the main component is ferric sulfate) in the waste dust is deposited in a catalyst inner pore canal; the process gas for absorbing and removing waste dust is cooled by a primary sulfur cooler 4 to recover elemental sulfur, and then is reheated by a primary converter reheater 5 to enter a primary converter 6 (the catalyst grading scheme is that 30 percent of LS-971 oxygen-removing catalyst is filled in the upper part, 60 percent of LS-981G organic sulfur hydrolysis catalyst is filled in the middle part, 10 percent of LSH-03A low-temperature high-activity hydrogenation catalyst is filled in the lower part), and H in the process gas is in the primary converter 6 2S and SO2 Claus reaction is carried out to recycle sulfur resources, organic sulfur in the process gas is hydrolyzed to generate hydrogen sulfide, and SO in the process gas 3 Is reduced to SO 2 The method comprises the steps of carrying out a first treatment on the surface of the The primary converter 6 is provided with an outlet process gasThe generated elemental sulfur is recovered by a secondary sulfur cooler 7, and is reheated by a secondary converter reheater 8 and then enters a secondary converter 9 (catalyst grading scheme: aluminum oxide-based sulfur recovery catalyst with large specific surface area of LS-02 is fully filled) to continuously undergo claus reaction to further recover sulfur resources; the process gas at the outlet of the secondary converter 9 is subjected to recovery of elemental sulfur by the tertiary sulfur cooler 10 to obtain Claus tail gas; the Claus tail gas is reheated to 220 ℃ by a hydrogenation tail gas reheater 11 and then enters a hydrogenation reactor 12, and sulfur-containing compounds are converted into H through hydrogenation under the action of a hydrogenation internal catalyst (LSH-03A) in the hydrogenation reactor 12 2 S, the generated hydrogenation tail gas is subjected to heat exchange condensation through a hydrogenation tail gas heat exchanger 13 and then enters a quenching tower 14 for cooling, the cooled hydrogenation tail gas enters an amine liquid absorption tower 15, and H in the hydrogenation tail gas is absorbed by amine liquid 2 S, generating purified tail gas; introducing part of the purified tail gas into a liquid sulfur pool 16 as gas stripping gas for liquid sulfur degassing, and introducing the gas stripping gas into a hydrogenation reactor 12 for treatment after the gas stripping gas for liquid sulfur degassing is extracted; the rest of purified tail gas is introduced into an incinerator 17 for incineration and then is discharged through a chimney 18.
The total sulfur conversion in this example was examined to be 97.16%; flue gas SO 2 60mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The iron content of the sulphur product was 0.0021% (m/m); the service life of the catalyst is more than 6 years.
Example 5
The process flow of the embodiment is shown in fig. 1, and the process of the embodiment is applied to a sulfur recovery device, and the device is an 80kt/a sulfur recovery device.
H 2 The method comprises the steps that (1) an acid gas with the S content of 55% is subjected to combustion reaction in a sulfur making furnace 1, an alkylated waste acid with the sulfuric acid content of 90% and the organic matter content of 10% is introduced into the sulfur making furnace to undergo a high-temperature cracking reaction, and natural gas is introduced as a combustion accompanying gas to ensure the normal reaction of the acid gas and the complete cracking of the waste acid, so that the temperature of the sulfur making furnace is controlled to be 950 ℃. The process gas at the outlet of the sulfur producing furnace 1 enters a waste dust adsorber 3 (the operation temperature is 320 ℃ C.) after part of heat is recovered by a waste heat boiler 2, LH-04 catalytic protection agent is filled in the waste dust adsorber, and waste dust (the main component is ferric sulfate) in the waste dust adsorber is deposited in a catalyst inner pore channel; the process gas after absorbing and removing the waste dust is cooled by a primary sulfur cooler 4 to recycle elemental sulfur and then is subjected to primary sulfur recoveryThe reheated gas enters a first-stage converter 6 (the catalyst grading scheme is that an upper part is filled with LS-971 oxygen-removing catalyst with the height of 35 percent, a middle part is filled with LS-981G organic sulfur hydrolysis catalyst with the height of 55 percent, and a lower part is filled with LSH-03A high-activity hydrogenation catalyst with the height of 10 percent), and H in the process gas is in the first-stage converter 6 2S and SO2 Claus reaction is carried out to recycle sulfur resources, organic sulfur in the process gas is hydrolyzed to generate hydrogen sulfide, and SO in the process gas 3 Is reduced to SO 2 The method comprises the steps of carrying out a first treatment on the surface of the The process gas at the outlet of the primary converter 6 is recycled to generate elemental sulfur through a secondary sulfur cooler 7, and enters a secondary converter 9 (catalyst grading scheme: fully filled with LS-02 alumina-based sulfur recycling catalyst with large specific surface area) after being reheated by a secondary converter reheater 8, claus reaction is continuously carried out, and sulfur resources are further recycled; the process gas at the outlet of the secondary converter 9 is subjected to recovery of elemental sulfur by the tertiary sulfur cooler 10 to obtain Claus tail gas; the Claus tail gas is reheated to 240 ℃ by a hydrogenation tail gas reheater 11 and then enters a hydrogenation reactor 12, and sulfur-containing compounds are converted into H through hydrogenation under the action of a hydrogenation internal catalyst (LSH-03A) in the hydrogenation reactor 12 2 S, the generated hydrogenation tail gas is subjected to heat exchange condensation through a hydrogenation tail gas heat exchanger 13 and then enters a quenching tower 14 for cooling, the cooled hydrogenation tail gas enters an amine liquid absorption tower 15, and H in the hydrogenation tail gas is absorbed by amine liquid 2 S, generating purified tail gas; introducing part of the purified tail gas into a liquid sulfur pool 16 as gas stripping gas for liquid sulfur degassing, and introducing the gas stripping gas into a hydrogenation reactor 12 for treatment after the gas stripping gas for liquid sulfur degassing is extracted; the rest of purified tail gas is introduced into an incinerator 17 for incineration and then is discharged through a chimney 18.
The total sulfur conversion in this example was found to be 97.05%; flue gas SO 2 82mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The iron content of the sulphur product was 0.0022% (m/m); the service life of the catalyst is more than 6 years.
Example 6
The process flow of the embodiment is shown in fig. 1, and the process of the embodiment is applied to a sulfur recovery device, and the device is an 80kt/a sulfur recovery device.
H 2 The acid gas with the S content of 68 percent is subjected to combustion reaction in the sulfur producing furnace 1, and the sulfuric acid content isThe high-temperature cracking reaction is carried out after the alkylated waste acid with 88 percent of organic matters and 12 percent of organic matters is introduced into the sulfur producing furnace, and the temperature of the sulfur producing furnace is controlled to be 1150 ℃ in order to ensure the normal reaction of the acid gas and the complete cracking of the waste acid, natural gas is introduced as the accompanying gas. The process gas at the outlet of the sulfur producing furnace 1 enters a waste dust adsorber 3 (the operation temperature is 360 ℃ C., and LH-04 catalyst protecting agent is filled in the waste dust adsorber) after part of heat is recovered by a waste heat boiler 2, and waste dust (the main component is ferric sulfate) in the waste dust is deposited in a catalyst inner pore channel; the process gas after absorbing and removing the waste dust is cooled by a first-stage sulfur cooler 4, is reheated by a first-stage converter reheater 5 and enters a first-stage converter 6 (the catalyst grading scheme is that an upper part is filled with 23% of LS-971 oxygen-removing catalyst, a middle part is filled with 62% of LS-981G organic sulfur hydrolysis catalyst, a lower part is filled with 15% of LSH-03A low-temperature high-activity hydrogenation catalyst), and H in the process gas is in the first-stage converter 6 2S and SO2 Claus reaction is carried out to recycle sulfur resources, organic sulfur in the process gas is hydrolyzed to generate hydrogen sulfide, and SO in the process gas 3 Is reduced to SO 2 The method comprises the steps of carrying out a first treatment on the surface of the The process gas at the outlet of the primary converter 6 is recycled to generate elemental sulfur through a secondary sulfur cooler 7, and enters a secondary converter 9 (catalyst grading scheme: fully filled with LS-02 alumina-based sulfur recycling catalyst with large specific surface area) after being reheated by a secondary converter reheater 8, claus reaction is continuously carried out, and sulfur resources are further recycled; the process gas at the outlet of the secondary converter 9 is subjected to recovery of elemental sulfur by the tertiary sulfur cooler 10 to obtain Claus tail gas; the Claus tail gas is reheated to 250 ℃ by a hydrogenation tail gas reheater 11 and then enters a hydrogenation reactor 12, and sulfur-containing compounds are converted into H through hydrogenation under the action of a hydrogenation internal catalyst (LSH-03A) in the hydrogenation reactor 12 2 S, the generated hydrogenation tail gas is subjected to heat exchange condensation through a hydrogenation tail gas heat exchanger 13 and then enters a quenching tower 14 for cooling, the cooled hydrogenation tail gas enters an amine liquid absorption tower 15, and H in the hydrogenation tail gas is absorbed by amine liquid 2 S, generating purified tail gas; introducing part of the purified tail gas into a liquid sulfur pool 16 as gas stripping gas for liquid sulfur degassing, and introducing the gas stripping gas into a hydrogenation reactor 12 for treatment after the gas stripping gas for liquid sulfur degassing is extracted; the rest of purified tail gas is introduced into an incinerator 17 for incineration and then is discharged through a chimney 18.
Through detection, the present embodimentThe total sulfur conversion of the plant in the examples was 97.02%; flue gas SO 2 Is 72mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The iron content of the sulphur product was 0.0025% (m/m); the service life of the catalyst is more than 6 years.
Comparative example 1
The process flow of this comparative example is shown in fig. 4, and the system configuration and process flow are the same as those of example 1, except that the waste adsorber 3 is not provided.
After the device of the comparative example was operated for a period of time, the reactor bed pressure drop was greatly increased, and the iron content in the produced sulfur was as high as 0.08% (m/m), and it was impossible to deliver smoothly. Continuing to operate, bed pressure drop increases, the plant is forced to shut down, and the discharged catalyst bed is packed with light pink dust.
Comparative example 2
The process flow of this comparative example is shown in fig. 1, and the system setup and process flow are the same as example 1, except that the catalyst grading scheme is: in the primary converter 6, the upper part is filled with 35% of LS-971 oxygen-removing catalyst, and the lower part is filled with 65% of LS-981G catalyst; the secondary converter 9 is fully charged with LS-02 catalyst.
The total sulfur conversion of the device described in this comparative example was 96.28%; flue gas SO 2 179mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The iron content of the sulphur product was 0.0026% (m/m); generating a part of SO by cracking waste acid 3 The part SO 3 Failure to handle the equipment causes serious corrosion of the equipment, and the equipment is forced to stop after 6 months of operation.
Comparative example 3
The process flow of this comparative example is shown in fig. 1, and the system setup and process flow are the same as example 1, except that the catalyst grading scheme is: in the primary converter 6, the upper part is filled with 35% of LS-02 catalyst, and the lower part is filled with 65% of LS-981G catalyst; the secondary converter 9 is fully charged with LS-02 catalyst.
The total sulfur conversion of the device described in this comparative example was 95.56%; flue gas SO 2 226mg/m 3 The method comprises the steps of carrying out a first treatment on the surface of the The iron content of the sulphur product was 0.0017% (m/m); because the sulfate of the catalyst is serious, the catalyst is used for three yearsIs forced to be replaced.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (8)
1. A system for preparing sulfur by efficiently treating alkylated waste acid is characterized by comprising a thermal reaction unit, a catalytic reaction unit and a tail gas purifying unit which are sequentially connected; wherein,
The thermal reaction unit includes:
sulfur production furnace (1), alkylated waste acid to be treated and H-containing 2 S, acid gas reacts in the sulfur producing furnace (1) to generate process gas containing elemental sulfur;
a waste dust absorber (3), wherein an iron-removing scale-containing catalyst is filled in the waste dust absorber (3) and is used for absorbing iron-containing waste dust in the process gas;
the sulfur cooler is used for condensing the process gas after adsorption treatment, sulfur in the process gas is collected, and the rest process gas enters the catalytic reaction unit;
the catalytic reaction unit includes:
a primary converter (6), wherein the primary converter (6) is filled with oxygen leakage removal catalyst, organic sulfur hydrolysis catalyst and hydrogenation catalyst, and the process gas can simultaneously perform Claus reaction, organic sulfur hydrolysis reaction and SO 3 Carrying out reduction reaction to obtain elemental sulfur and catalytic tail gas;
the secondary converter (9) is filled with a sulfur recovery catalyst, and the catalytic tail gas is subjected to Claus catalytic conversion to obtain elemental sulfur and Claus tail gas;
the purifying exhaust gas unit includes:
a hydrogenation reactor (12), wherein the Claus tail gas is arranged in the hydrogenation reactor12 Hydrogenation of sulfur-containing compounds to H) 2 S, obtain H-containing 2 S, hydrogenation tail gas;
an absorption tower (15), wherein the absorption tower (15) is used for absorbing H in the hydrogenation tail gas 2 S, obtaining purified tail gas;
a tail gas incinerator (17) for incinerating and discharging the purified tail gas;
wherein, in the primary converter (6), the upper part is filled with oxygen-leaking catalyst with the height of 20-40%, the middle part is filled with organic sulfur hydrolysis catalyst with the height of 45-75%, and the lower part is filled with low-temperature high-activity hydrogenation catalyst with the height of 5-15%.
2. The system for preparing sulfur by efficiently treating alkylated waste acid according to claim 1, wherein a waste heat boiler (2) is further arranged between the sulfur producing furnace (1) and the waste dust adsorber (3) for recovering part of heat.
3. The system for preparing sulfur by efficiently treating alkylated waste acid according to claim 1 or 2, wherein the sulfur cooler is arranged after the primary converter (6) and the secondary converter (9), respectively.
4. The system for preparing sulfur by efficiently treating alkylated waste acid according to claim 1 or 2, wherein a primary converter reheater (5) and a secondary converter reheater (8) are further arranged before the primary converter (6) and the secondary converter (9), respectively.
5. A process for preparing sulfur based on the efficient treatment of alkylated waste acid by the system of any of claims 1-4, comprising the steps of:
(1) Will contain H 2 S acid gas and alkylated waste acid to be treated are introduced into the sulfur producing furnace (1), and the sulfur producing furnace contains H 2 S acid gas is combusted and converted into SO in the sulfur producing furnace (1) 2 The alkylated waste acid is generated by high-temperature pyrolysisSO 2 And a small amount of SO 3 The method comprises the steps of carrying out a first treatment on the surface of the The H obtained 2 S and SO 2 The Claus reaction takes place to produce a process gas containing elemental sulphur; inputting the process gas into the waste dust adsorber (3), and removing waste dust of the process gas through catalysis; the process gas after adsorption treatment enters the sulfur cooler to be condensed to obtain liquid sulfur and is collected, and the process gas after collecting the liquid sulfur continuously enters the catalytic reaction unit;
(2) The process gas enters the primary converter (6) and is subjected to the Claus reaction, the organic sulfur hydrolysis reaction and the SO simultaneously under the action of a selected catalyst 3 Carrying out reduction reaction to obtain elemental sulfur and catalytic tail gas; collecting elemental sulfur and continuing the obtained catalytic tail gas into the secondary converter (9), and performing Claus catalytic conversion under the action of a selected catalyst to obtain elemental sulfur and Claus tail gas, wherein the Claus tail gas enters the tail gas purifying unit;
(3) The Claus tail gas is subjected to a hydrogenation catalytic reaction in the hydrogenation reactor (12) to convert sulfur-containing compounds therein into H 2 S enters an absorption tower (15) to absorb H 2 S, S; the purified tail gas is introduced into the tail gas incinerator (17) and is discharged after being incinerated.
6. The process for preparing sulfur by efficiently treating alkylated waste acid according to claim 5, wherein said step (1) further comprises the step of introducing natural gas as a co-firing gas into said sulfur producing furnace (1).
7. The process for preparing sulfur by efficiently treating alkylated waste acid according to claim 5 or 6, wherein said step (2) further comprises the step of condensing the obtained elemental sulfur and tail gas in a sulfur cooler after catalytic reaction in said primary converter (6) and said secondary converter (9) and collecting liquid sulfur.
8. The process for producing sulfur by efficiently treating alkylated waste acid according to claim 7, further comprising the step of heating the corresponding process gas before entering the primary converter (6), the secondary converter (9) and the hydrogenation reactor (12).
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| US4826670A (en) * | 1985-03-20 | 1989-05-02 | Air Products And Chemicals, Inc. | Oxygen enriched claus system with sulfuric acid injection |
| CN104249995A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Method for reducing SO2 emission concentration of sulfur recovery device |
| CN204848269U (en) * | 2015-06-17 | 2015-12-09 | 中国石油化工股份有限公司 | A alkanisation spent acid spray gun and sulphur recovery unit for sulphur recovery unit |
| CN106315518A (en) * | 2015-06-17 | 2017-01-11 | 中国石油化工股份有限公司 | Alkylation waste acid treatment apparatus and method |
| CN106586972A (en) * | 2015-10-15 | 2017-04-26 | 中国石油化工股份有限公司 | Energy-saving, environmental-protection and low-emission sulfur recovery process |
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| US9758376B2 (en) * | 2013-06-21 | 2017-09-12 | Phillips 66 Company | Process for degassing condensed sulfur from a Claus sulfur recovery system |
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| US4826670A (en) * | 1985-03-20 | 1989-05-02 | Air Products And Chemicals, Inc. | Oxygen enriched claus system with sulfuric acid injection |
| CN104249995A (en) * | 2013-06-25 | 2014-12-31 | 中国石油化工股份有限公司 | Method for reducing SO2 emission concentration of sulfur recovery device |
| CN204848269U (en) * | 2015-06-17 | 2015-12-09 | 中国石油化工股份有限公司 | A alkanisation spent acid spray gun and sulphur recovery unit for sulphur recovery unit |
| CN106315518A (en) * | 2015-06-17 | 2017-01-11 | 中国石油化工股份有限公司 | Alkylation waste acid treatment apparatus and method |
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