CN113860265A - 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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- CN113860265A CN113860265A CN202010622401.6A CN202010622401A CN113860265A CN 113860265 A CN113860265 A CN 113860265A CN 202010622401 A CN202010622401 A CN 202010622401A CN 113860265 A CN113860265 A CN 113860265A
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- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 353
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 301
- 239000011593 sulfur Substances 0.000 title claims abstract description 300
- 239000002699 waste material Substances 0.000 title claims abstract description 172
- 239000002253 acid Substances 0.000 title claims abstract description 120
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 203
- 238000000034 method Methods 0.000 claims abstract description 143
- 230000008569 process Effects 0.000 claims abstract description 134
- 238000006243 chemical reaction Methods 0.000 claims abstract description 91
- 239000000428 dust Substances 0.000 claims abstract description 69
- 238000011084 recovery Methods 0.000 claims abstract description 65
- 238000012545 processing Methods 0.000 claims abstract description 8
- 239000006096 absorbing agent Substances 0.000 claims abstract description 6
- 239000007789 gas Substances 0.000 claims description 280
- 238000005984 hydrogenation reaction Methods 0.000 claims description 115
- 239000007788 liquid Substances 0.000 claims description 63
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 49
- 125000001741 organic sulfur group Chemical group 0.000 claims description 42
- 230000003197 catalytic effect Effects 0.000 claims description 33
- 238000006460 hydrolysis reaction Methods 0.000 claims description 31
- 229910052742 iron Inorganic materials 0.000 claims description 28
- 230000000694 effects Effects 0.000 claims description 27
- 238000006555 catalytic reaction Methods 0.000 claims description 24
- 230000007062 hydrolysis Effects 0.000 claims description 21
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 18
- 238000010521 absorption reaction Methods 0.000 claims description 16
- 230000009471 action Effects 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 13
- 238000006722 reduction reaction Methods 0.000 claims description 13
- 239000002918 waste heat Substances 0.000 claims description 12
- 238000005804 alkylation reaction Methods 0.000 claims description 11
- 238000000197 pyrolysis Methods 0.000 claims description 10
- 239000000567 combustion gas Substances 0.000 claims description 9
- 239000003345 natural gas Substances 0.000 claims description 9
- 238000000746 purification Methods 0.000 claims description 9
- 230000029936 alkylation Effects 0.000 claims description 8
- 238000009833 condensation Methods 0.000 claims description 8
- 230000005494 condensation Effects 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 5
- 238000001179 sorption measurement Methods 0.000 claims description 5
- 239000005864 Sulphur Substances 0.000 claims description 3
- 238000007599 discharging Methods 0.000 claims description 2
- 238000005336 cracking Methods 0.000 abstract description 19
- 238000010409 ironing Methods 0.000 abstract description 8
- 238000005260 corrosion Methods 0.000 abstract description 7
- 230000007797 corrosion Effects 0.000 abstract description 6
- 231100000572 poisoning Toxicity 0.000 abstract description 5
- 230000000607 poisoning effect Effects 0.000 abstract description 5
- 239000003208 petroleum Substances 0.000 abstract description 3
- 238000013461 design Methods 0.000 abstract description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 57
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 32
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 26
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 24
- AKEJUJNQAAGONA-UHFFFAOYSA-N sulfur trioxide Chemical compound O=S(=O)=O AKEJUJNQAAGONA-UHFFFAOYSA-N 0.000 description 20
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 15
- 150000001412 amines Chemical class 0.000 description 15
- 238000007872 degassing Methods 0.000 description 15
- 239000003546 flue gas Substances 0.000 description 15
- 239000011148 porous material Substances 0.000 description 13
- 239000002912 waste gas Substances 0.000 description 13
- 238000002485 combustion reaction Methods 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 10
- 238000010791 quenching Methods 0.000 description 10
- 239000003223 protective agent Substances 0.000 description 9
- 238000001816 cooling Methods 0.000 description 7
- 238000001514 detection method Methods 0.000 description 7
- 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
- 230000000171 quenching effect Effects 0.000 description 7
- 230000007613 environmental effect Effects 0.000 description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 5
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 5
- 239000012535 impurity Substances 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 239000001301 oxygen Substances 0.000 description 5
- 238000011049 filling Methods 0.000 description 4
- 230000003301 hydrolyzing effect Effects 0.000 description 4
- 239000005416 organic matter Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 238000010306 acid treatment Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 3
- 230000009467 reduction Effects 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
- 230000002378 acidificating effect Effects 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
- 238000006392 deoxygenation reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 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
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 230000019635 sulfation Effects 0.000 description 2
- 238000005670 sulfation reaction Methods 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- 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
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 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
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000002902 bimodal effect Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 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
- 239000001282 iso-butane Substances 0.000 description 1
- 239000002932 luster 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
- 238000012856 packing Methods 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000011573 trace mineral Substances 0.000 description 1
- 235000013619 trace mineral Nutrition 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/0027—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions
- 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
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B17/0426—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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- 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
- C01B17/0447—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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
- Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
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. The system for preparing the sulfur by efficiently treating the alkylated waste acid can utilize the conventional sulfur recovery deviceThe method realizes the treatment of the alkylated waste acid, and saves a large amount of cost compared with other existing methods for treating the alkylated waste acid; waste dust absorbers filled with the de-ironing scale-containing catalysts are additionally arranged to absorb waste dust generated by cracking of waste acid to get out of the way, so that the problems of catalyst poisoning and subsequent equipment blockage caused by the waste dust are prevented; moreover, the reasonable grading design is carried out on the catalyst in the two-stage conversion reactor, SO in the high-temperature process gas is reasonably treated3The device corrosion problem which may be 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 realized, 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 has high octane number and small sensitivity (difference between research octane number and 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 automotive gasoline, and has increasingly prominent importance particularly along with urgent needs of gasoline quality upgrading and higher environmental protection requirement standards.
At present, most of the oil refineries in China adopt a sulfuric acid alkylation process using concentrated sulfuric acid as a catalyst, and 80-100kg of waste sulfuric acid with the concentration of 80% -85% is produced when 1t of hydrocarbonated oil is produced by the process. Among the waste sulfuric acids produced. The waste sulfuric acid is a colloidal liquid with high viscosity, contains 8-14% of organic matters (polymerized oil) and water besides sulfuric acid, is black and red in color and luster, unstable in property, emits special odor, is difficult to treat, cannot be utilized, and brings serious pollution to the ecological environment. Therefore, how to solve the problem of rational treatment of waste acid is also a key technology for limiting the development of the sulfuric acid alkylation process.
At present, the conventional treatment mode of sulfuric acid alkylation waste acid mainly comprises the following steps: preparing industrial sulfuric acid, producing white carbon black or producing ammonium sulfate and the like through high-temperature thermal cracking; the high-temperature thermal cracking method is the most commonly used waste acid treatment process for alkylation devices at home and abroad at present, but the equipment material requirement is high, the process flow is complex, so the investment of single-system equipment is large, the data introduction is provided, and a set of waste acid combustion cracking recovery device with the treatment capacity of 1 ten thousand tons per year at least needs 1 hundred million investments, so the waste acid combustion cracking recovery device is not suitable for actual production; the method for preparing precipitated white carbon black and a petroleum antirust agent by using the alkylated waste sulfuric acid or producing ammonium sulfate by using the alkylated waste sulfuric acid and ammonia water has the advantages of simple process and low investment, but the oil (polymerization oil) separated in the reaction process cannot be effectively treated, and is still a pollution source.
In order to solve the problems, most oil refineries in China are matched with 2-3 sets of sulfur recovery devices, and the recovery treatment is realized by directly introducing waste acid into the sulfur recovery devices: the alkylated waste acid is introduced into a sulfur production furnace of a sulfur device and is decomposed at high temperature to generate sulfur dioxide, and the sulfur dioxide and hydrogen sulfide are further subjected to claus reaction under the action of a sulfur recovery catalyst in a sulfur production unit to generate elemental sulfur, so that the sulfur resource is recycled. The scheme can be used for recovering waste acid by depending on the conventional sulfur recovery unit, does not need to establish a separate waste acid recovery device, saves investment and has great advantages; moreover, the treatment capacity of the waste acid is large, the limited condition is small, no secondary pollution is generated, the requirement of an environment-friendly process is met, and the waste acid recycling process becomes the preferred waste acid recycling process of most of oil refineries at present.
However, because the alkylated waste acid contains a certain amount of organic matters and a small amount of iron, the catalyst is deposited carbon inevitably along with incomplete combustion of the organic matters, and the normal operation of the sulfur recovery device is influenced; in addition, the existence of iron can generate a large amount of waste dust to influence the performance of the catalyst on one hand, and can increase the iron content in the sulfur product on the other hand, so that the iron content of the sulfur product exceeds the standard; in addition, the waste acid can have a small amount of sulfur trioxide in the process gas after the high-temperature cracking in the sulfur recovery furnace, and if the part of sulfur trioxide can not be processed in time, serious corrosion problems can be brought to sulfur device equipment in the subsequent process. For example, Chinese patent CN102951614A discloses a method for filling 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; for another example, chinese patent CN102951613A discloses a catalyst grading method for a sulfur recovery device for acid gas treatment, the overall service life of the graded catalyst can reach 6 years, and the flue gas emission reaches the standard; for another example, chinese patent CN101659400A discloses a catalyst combination process for 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 recovering and treating sulfur, but if the catalyst grading scheme is adopted when the alkylated waste acid is treated by a sulfur device, the problems of over standard of iron content of a sulfur product, coking of the catalyst and the like can occur, meanwhile, the total sulfur conversion rate of the device is reduced, and the service life of the catalyst is shortened.
In order to improve the problems, Chinese patent CN106256760A discloses a process for treating alkylated waste acid by using a sulfur device, which realizes the low-investment and high-efficiency treatment of the alkylated waste acid; reasonably treats SO in high-temperature process gas3Avoiding the corrosion problem of the device, SO3The conversion rate reaches more than 97 percent; meanwhile, the influence of residual iron in waste acid can be eliminated, and the iron content in the sulfur product is less than 0.005 percent; eliminate the influence of carbon deposit on the catalyst and effectively protect the Claus catalyst. The catalyst can maintain high Claus catalytic activity and organic sulfur waterThe activity is decomposed, and the total sulfur conversion rate of the device reaches over 96.5 percent. However, as the process requirements continue to increase, the following problems still exist in the process:
firstly, the device cannot meet the requirement of flue gas SO2Emission to reach the standard, along with the environment worsens day by day, the environmental protection regulation in China is stricter day by day, 2015 in China issues a new environmental protection standard, emission standard of pollutants for petroleum refining industry (GB31570-2015), wherein the regulation is as follows: flue gas SO of sulfur device2The emission concentration limit value is required to reach 400mg/Nm in general areas3In the following, the requirement of the key area is 100mg/Nm3The following; and sulfur tail gas SO2The emission is also one of important indexes in the checking and accounting of the total pollutant amount of the ministry of environmental protection, a newly-built sulfur device 2015 is executed from 7 months and 1 days, and an old sulfur device is executed from 2017 months and 1 days. The upper part of a primary converter in the process device is filled with 5-30% of a deferrization and scale-holding protective agent, which is equivalent to that the consumption of the Claus catalyst of the whole device is reduced by 5-30%, and the conversion rate of a part of the device, especially the conversion rate of organic sulfur, can be reduced, thereby causing the flue gas SO of the device2The latest environmental protection regulation requirements cannot be met;
secondly, the scale holding capacity of the de-ironing scale holding catalyst in the device is limited, the long-period operation of the device can be influenced, although the scale holding capacity of the de-ironing scale holding catalyst filled in the process can reach 30%, the alkylation device generally has a serious corrosion problem, the impurity content in waste acid is high, and according to knowledge, 1kg of waste dust (the main component is ferric sulfate) can be generated per hour under the normal operation condition of the 3.5 ten thousand ton/year waste acid cracking device; therefore, once the alkylation device fluctuates and the impurity content in the waste acid is too high, the iron-removing and scale-holding catalyst is easy to lose efficacy, so that the normal operation of the catalyst of the sulfur recovery device is influenced, and the unplanned shutdown of the sulfur device is caused in serious cases;
in addition, the de-ironing scale-holding catalyst is filled in a reactor of the device and cannot be treated independently, once the de-ironing scale-holding catalyst has a problem in the use process, the whole device needs to be shut down to process the problem, and great operation hidden trouble 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 need to be further perfected, and a treatment device and a process for efficiently treating the alkylated waste acid are further developed, so that the device and the process have positive significance.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to provide a recovery device for preparing sulfur from alkylated waste acid, SO as to eliminate the influence on the normal operation of the device after the alkylated waste acid is introduced into a sulfur device, eliminate the influence on the catalyst of the sulfur recovery device, the quality of sulfur products, device equipment and the like possibly caused by the treatment of the alkylated waste acid in the sulfur recovery device, and solve the problem that the alkylated waste acid is introduced into the flue gas SO of the sulfur device2The discharge does not reach the standard, the long-period normal operation of the sulfur recovery device is ensured, and the practical problem that the waste acid treatment of the existing alkylation device and a newly-built alkylation device is difficult is solved;
the second technical problem to be solved by the invention is to provide a recovery process for preparing sulfur from alkylated waste acid, which can meet the requirement of processing 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 discharge of the device and ensure the long-period operation of the sulfur recovery device.
In order to solve the technical problem, the system for efficiently treating the alkylated waste acid to prepare the sulfur comprises a thermal reaction unit, a catalytic reaction unit and a tail gas purification unit which are sequentially connected; wherein,
the thermal reaction unit includes:
sulfur furnace, alkylated waste acid to be treated and H-containing2The acid gas of the S reacts in the sulfur production furnace to generate process gas containing elemental sulfur;
the waste dust adsorber is filled with a de-ironing scale-holding catalyst and is used for adsorbing iron-containing waste dust in the process gas;
the sulfur cooler is used for condensing the process gas subjected to adsorption treatment in the sulfur cooler, collecting condensed liquid sulfur, and feeding the residual process gas into the catalytic reaction unit;
the catalytic reaction unit includes:
a first-stage converter filled with oxygen-eliminating catalyst, organic sulfur hydrolyzing catalyst and hydrogenating catalyst, and the process gas can simultaneously perform Claus reaction, organic sulfur hydrolyzing reaction and SO reaction3Carrying out reduction reaction to obtain elemental sulfur and catalytic tail gas;
a secondary converter, wherein a sulfur recovery catalyst is filled in the secondary converter, and the catalytic tail gas is subjected to Claus catalytic conversion to obtain elemental sulfur and Claus tail gas;
the tail gas purifying unit comprises:
a hydrogenation reactor in which said Claus tail gas hydrogenates sulfur-containing compounds to H2S, obtaining a product containing H2Hydrogenation tail gas of S;
an absorption tower for absorbing H in the hydrogenation tail gas2S, obtaining purified tail gas;
and the tail gas incinerator is used for incinerating and discharging the purified tail gas.
The waste dust adsorber is 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 a secondary converter of a catalytic reaction unit is protected, and downstream equipment is prevented from being blocked. Preferably, two waste dust adsorbers are arranged, one is opened and the other is prepared, and the waste dust adsorbers can be opened and shut down at any time so as to prevent catalyst poisoning and subsequent equipment blockage caused by waste dust generated by waste acid cracking. The pressure drop rise of the waste dust adsorber indicates that the scale capacity of the de-ironing scale-holding catalyst in the adsorber is close to saturation, and at the moment, the spare adsorber needs to be replaced in time, and meanwhile, the catalyst of the adsorber needs to be replaced. The operating temperature of the waste dust adsorber is 280-350 ℃. The scale holding capacity of the iron-removing scale holding catalyst is more than 30 percent.
Specifically, in the waste dust adsorber:
the de-iron scale holding catalyst can be any feasible de-iron catalyst with de-iron function in the prior art, the specific filling amount is determined according to the scale of the device and the amount of waste dust, no fixed requirement exists, and the de-iron scale holding catalyst can be large or small, is small in size and is frequently replaced, and is large in size and is not required to be frequently replaced.
Specifically, a waste heat boiler is arranged between the sulfur production furnace and the waste dust adsorber and is used for recovering partial heat.
Specifically, in the first-stage converter, the oxygen-leakage-removal catalyst is filled at the top position, the organic sulfur hydrolysis catalyst is filled at the middle position, and the hydrogenation catalyst is filled at the bottom position.
wherein ,
the oxygen-leakage-removing catalyst is any Claus sulfur recovery catalyst with the oxygen-leakage-removing function;
the organic sulfur hydrolysis catalyst can be any Claus sulfur recovery catalyst with higher organic sulfur hydrolysis rate;
the hydrogenation catalyst can be any low-temperature tail gas hydrogenation catalyst;
the sulfur recovery catalyst may be any sulfur recovery catalyst having a higher activity.
In particular, small amounts of SO are produced as a result of the cracking of the spent alkylation acid in sulfur furnaces3，SO3The paint has strong corrosiveness, and can cause corrosion of subsequent equipment; moreover, the introduction of the alkylated waste acid into a sulfur device for treatment can cause the reduction of the Claus conversion rate in a sulfur production furnace, and organic polymers contained in the waste acid can generate part of organic sulfur in the cracking process, SO that the filling of the catalysts in the primary converter and the secondary converter is preferably carried out according to a certain grading scheme, and on one hand, the SO generated by the cracking of the waste acid is ensured3Reduction to SO2On the other hand, the normal operation of the Claus and organic sulfur reaction of the sulfur device is ensured, and the smoke emission of the device is ensured to reach the standard so as to ensure the normal operation of the device.
Specifically, in the first-stage converter, the upper part is filled with 20-40% of the height of the oxygen-removing catalyst, the middle part is filled with 45-75% of the height of the catalyst of organic sulfur hydrolysis, and the lower part is filled with 5-15% of the height of the low-temperature high-activity hydrogenation catalyst. This is mainly because: the upper part of the first-stage converter is filled with an oxygen-removing catalyst which can remove oxygen leakage in the process gas and protect the catalyst from sulfation and alkylationAfter the waste acid is introduced into a sulfur recovery device for treatment, in order to ensure complete cracking of the alkylated waste acid, the air distribution quantity of a sulfur production furnace needs to be increased, oxygen leakage is likely to exist, the catalyst can be effectively protected by using the oxygen leakage removal catalyst, and the reduction of the reaction activity caused by catalyst sulfation is prevented; the middle part of the primary converter is filled with the organic sulfur hydrolysis catalyst, 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 first-stage converter is filled with a low-temperature high-activity hydrogenation catalyst which can crack waste acid to generate SO3Reduction to SO2Elimination of SO3Corrosion of subsequent equipment.
The secondary converter is completely filled with the 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 completely filled with a low-temperature high-activity hydrogenation catalyst, so that H in the Claus tail gas can be removed2And the sulfur-containing compounds except S are fully hydrogenated or hydrolyzed, so that the device is ensured to have higher sulfur recovery rate.
Specifically, a sulfur cooler is respectively arranged behind the first converter and the second converter.
Specifically, a primary converter reheater and a secondary converter reheater are respectively arranged in front of the first converter and the second converter.
The invention also discloses a process for efficiently treating the alkylated waste acid to prepare sulfur based on the system, which comprises the following steps:
(1) will contain H2Introducing the acidic gas of S and the alkylated waste acid to be treated into the sulfur production furnace, wherein the acidic gas contains H2The acid gas of S is converted into SO by partial combustion in the sulfur production furnace2The alkylated waste acid undergoes pyrolysis to generate SO2And a small amount of SO3(ii) a Obtained H2S and SO2A Claus reaction takes place to generate a process gas containing elemental sulphur; feeding the process gas into the waste dust adsorber, and removing the process gas by catalysisDust in the process gas; the process gas after adsorption treatment enters the sulfur cooler and is condensed to obtain liquid sulfur which is collected, and the process gas continuously enters the catalytic reaction unit;
(2) the process gas enters the first converter and simultaneously carries out Claus reaction, organic sulfur hydrolysis reaction and SO under the action of a selected catalyst3Carrying out reduction reaction to obtain elemental sulfur and catalytic tail gas; collecting elemental sulfur, continuously introducing the obtained catalytic tail gas into the second converter, performing Claus catalytic conversion under the action of a selected catalyst to generate elemental sulfur and Claus tail gas, and collecting the elemental sulfur, 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 H2S, and enters an absorption tower to absorb H2S; the purified tail gas is introduced into the tail gas incinerator and is discharged after incineration.
Specifically, the step (1) further comprises the step of introducing natural gas as the secondary combustion gas into the sulfur production furnace.
Specifically, the step (2) further comprises the 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 efficiently treating the alkylated waste acid to prepare the sulfur, the alkylated waste acid can be treated by using the conventional sulfur recovery device, and compared with other conventional alkylated waste acid treatment methods, a large amount of cost is saved; the system comprises a thermal reaction unit, a catalytic reaction unit and a tail gas purification unit, and waste dust absorbers filled with de-ironing scale-holding catalysts are additionally arranged to absorb waste dust generated by cracking of waste acid, so that the problems of catalyst poisoning and subsequent equipment blockage caused by the waste dust are prevented; and, by making sense of the catalyst in the two-stage conversion reactorThe grading design reasonably treats SO in high-temperature process gas3The device corrosion problem which may be 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 realized, and the long-period operation of the sulfur recovery device is ensured. The system can realize that the iron content in the sulfur product of the device is less than 0.005 percent; the total sulfur conversion rate of the device reaches more than 97.0 percent; flue gas SO of device2The discharge is less than 100mg/m3(ii) a 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, the upper part of the primary converter is filled with 20-40% of the height of the oxygen-removing catalyst, the middle part of the primary converter is filled with 45-75% of the height of the catalyst of organic sulfur hydrolysis, and the lower part of the primary converter is filled with 5-15% of the height of the low-temperature high-activity hydrogenation catalyst; the secondary converter is completely filled with the alumina-based sulfur recovery catalyst with large specific surface area; the tail gas hydrogenation converter is completely filled with a low-temperature high-activity hydrogenation catalyst. On one hand, SO generated by cracking of waste acid is ensured3Reduction to SO2On the other hand, the normal operation of the Claus and organic sulfur reaction of the sulfur device is ensured, and the smoke of the device is ensured to be discharged up to the standard. Through detection, in the whole catalytic conversion reaction, SO3The conversion rate reaches more than 97 percent; effectively improves the sulfur recovery efficiency of the device and the flue gas SO of the device2The discharge is less than 100mg/m3The influence of waste acid introduction on the operation of the device is eliminated.
Drawings
In order that the present disclosure may be more readily and clearly understood, the following detailed description of the present disclosure is provided in connection with specific embodiments thereof and the accompanying drawings, in which,
FIG. 1 is a schematic diagram of the system of the present invention;
FIG. 2 is a schematic illustration of the catalyst loading in the primary converter of the present invention;
FIG. 3 is a schematic illustration of the packing of the catalyst in the secondary converter of the present invention;
FIG. 4 is a flow chart of the treatment process in comparative example 1;
the reference numbers in the figures denote: 1-a sulfur production furnace, 2-a waste heat boiler, 3-a waste dust adsorber, 4-a primary sulfur cooler, 5-a primary converter reheater, 6-a primary converter, 7-a secondary sulfur cooler, 8-a secondary converter reheater, 9-a secondary converter, 10-a tertiary sulfur cooler, 11-a tail gas reheater, 12-a hydrogenation reactor, 13-a hydrogenation tail gas heat exchanger, 14-a quench tower, 15-an absorption tower, 16-a liquid sulfur pool, 17-a tail gas incinerator and 18-a chimney.
Detailed Description
The structure of the system for efficiently treating alkylated waste acid to prepare sulfur according to the invention is schematically shown in fig. 1, and the system comprises a thermal reaction unit, a catalytic reaction unit and a tail gas purification unit which are connected in sequence; wherein,
the thermal reaction unit includes:
sulfur production furnace 1, alkylated waste acid to be treated and H-containing2The acid gas of S reacts in the sulfur production furnace 1 to generate process gas containing elemental sulfur;
a waste heat boiler 2, wherein the generated process gas recovers part of heat through the waste heat boiler 2;
a waste dust adsorber 3, wherein a de-iron scale-holding catalyst is filled in the waste dust adsorber 3, and iron-containing waste dust generated by impurities in the alkylated waste acid is captured in a catalyst pore channel and is used for the iron-containing waste dust in the process gas;
the primary sulfur cooler 4 is used for condensing the process gas subjected to adsorption and filtration treatment in the primary sulfur cooler 4, collecting the condensed liquid sulfur and feeding the collected liquid sulfur into a liquid sulfur pool 16, and feeding the process gas into 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 subjected to heating treatment in the primary converter reheater 5;
the primary converter 6 is filled with a deoxygenation catalyst, an organic sulfur hydrolysis catalyst and a low-temperature high-activity hydrogenation catalyst; the process gas entering the primary converter 6 can simultaneously carry out Claus reaction, organic sulfur hydrolysis reaction and SO3Carrying out reduction reaction to respectively obtain elemental sulfur and catalytic tail gas; as shown in fig. 2The filling schematic diagram of the agent is that the upper part of the primary converter 6 is filled with 20-40% of the height of the oxygen-removing catalyst, the middle part is filled with 45-75% of the height of the organic sulfur hydrolysis catalyst, and the lower part is filled with 5-15% of the height of the low-temperature high-activity hydrogenation catalyst;
the secondary sulfur cooler 7 is used for condensing the elemental sulfur and the catalytic tail gas which are subjected to the catalytic reaction by the primary converter 6 in the secondary sulfur cooler 7, collecting the obtained liquid sulfur and feeding the collected liquid sulfur into the liquid sulfur pool 16, and continuously reacting the condensed catalytic tail gas;
a secondary converter reheater 8, in which the catalytic exhaust gas is subjected to a heating treatment;
a secondary converter 9, as shown in the schematic catalyst loading diagram shown in fig. 3, wherein the secondary converter 9 is completely filled with a large-specific-surface-area alumina-based sulfur recovery catalyst, and the catalytic tail gas is subjected to Claus catalytic conversion to obtain elemental sulfur and Claus tail gas;
the third-stage sulfur cooler 10 is used for condensing the elemental sulfur and the Claus tail gas which are subjected to the catalytic reaction by the second-stage converter 9 in the third-stage sulfur cooler 10, collecting the obtained liquid sulfur and feeding the collected liquid sulfur into the liquid sulfur tank 16, and continuously feeding the condensed Claus tail gas into a subsequent tail gas purification unit;
the tail gas purifying unit comprises:
the tail gas reheater 11 is used for heating the separated Claus tail gas entering the tail gas reheater 11;
a hydrogenation reactor 12, wherein a low-temperature high-activity hydrogenation catalyst is completely filled in the hydrogenation reactor 12, and the heated Claus tail gas is used for hydrogenating and converting sulfur-containing compounds into H in the hydrogenation reactor 122S, can ensure H removal from Claus tail gas2Fully hydrogenating or hydrolyzing sulfur-containing compounds except S to obtain H2Hydrogenation tail gas of S;
hydrogenation tail gas heat exchanger 13, H-containing obtained after reaction2The hydrogenation tail gas of the S is subjected to heat exchange treatment through the hydrogenation tail gas heat exchanger 13;
a quench tower 14 containing H2The hydrogenation tail gas of the S enters the quenching tower 14 for cooling treatment;
an absorption tower 15, wherein amine liquid is arranged in the absorption tower 15 and is used for absorbing H in the hydrogenation tail gas2S, further obtaining purified tail gas;
the liquid sulfur pool 16 is used for absorbing liquid sulfur obtained by condensation of the sulfur coolers;
and the tail gas incinerator 17 incinerates the tail gas purified by the absorption tower 15 and discharges the tail gas through a chimney 18.
Based on a system shown in the attached figure 1, the process for efficiently treating the alkylated waste acid to prepare the sulfur comprises the following steps:
(1) the thermal reaction unit is as follows: containing H2The acid gas of S is partially combusted and converted into SO in the sulfur production furnace2The alkylated waste acid to be treated is pyrolyzed in the sulfur production furnace 1 to generate SO2And a small amount of SO3Because the acid gas, the waste acid and the air are mixed and combusted in the sulfur production furnace, in order to ensure that the acid gas normally reacts and the alkylated waste acid is cracked completely, partial natural gas is introduced into the sulfur production furnace to be used as co-combustion gas, the combustion temperature is controlled to 950 ℃ and 1400 ℃, and partial H is controlled2Conversion of S to SO by combustion2Cracking waste acid at high temperature to generate SO2，H2S and SO2Claus reaction is carried out at high temperature to generate process gas (containing elemental sulfur and H) containing elemental sulfur2S、SO2、SO3And COS, CS2And partial waste dust), the process gas enters a waste dust absorber 3 after partial 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 absorber 3 enters the primary sulfur cooler 4 for condensation, the liquid sulfur obtained by condensation is separated from the process gas and then enters the liquid sulfur pool 16, and the separated process gas enters the subsequent catalytic reaction unit;
the thermal reaction unit relates to a reaction process comprising:
2H2S+3O2→2SO2+2H2O (1)
2H2SO4→2SO2+2H2O+O2 (2)
SO2+2H2S→2H2O+3S (3)
(2) the catalytic reaction unit is as follows: the separated process gas is heated by the reheater 5 of the primary converter, enters the primary converter 6, reacts under the action of a selected graded catalyst, and simultaneously carries out Claus reaction, organic sulfur hydrolysis reaction and SO3Reduction reaction, the hydrogen sulfide and sulfur dioxide take the Claus reaction to generate elemental sulfur, the organic sulfur takes the hydrolysis reaction to generate hydrogen sulfide and SO3Reduction reaction is carried out to generate SO2The reacted catalytic tail gas enters the secondary sulfur cooler 7 for condensation, the elemental sulfur enters the liquid sulfur pool 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 for reaction, and the catalytic tail gas is subjected to Claus catalytic conversion under the action of a catalyst to generate elemental sulfur and Claus tail gas; the elemental sulfur and Claus tail gas enter the three-stage sulfur cooler for condensation, the liquid sulfur generated after condensation also enters a liquid sulfur pool 16, and the Claus tail gas (containing trace element sulfur and H) after condensation2S、SO2And COS, CS2Sulfides) enters a subsequent tail gas purification unit;
the catalytic reaction unit relates to a reaction process comprising the following steps:
SO2+2H2S→2H2O+3S (4)
COS+H2O→H2S+CO2 (5)
CS2+2H2O→2H2S+CO2 (6)
SO3+CO→SO2+CO2 (7)
(3) the tail gas purification unit is as follows: the condensed Claus tail gas is heated to 200-300 ℃ by a tail gas reheater 11, and enters the hydrogenation reactor 12 to carry elemental sulfur and SO under the action of the hydrogenation catalyst2All of the hydrogen is converted into H2S，COS、CS2Conversion to H by hydrolysis2S; then enters an absorption tower 15 containing amine liquid after heat exchange of a hydrogenation tail gas heat exchanger 12 and temperature reduction of a quench tower 13, and the amine liquid absorbs H in the hydrogenation tail gas2S; the obtained purified tail gas can be introduced into the liquid sulfur pool 16 to be used as stripping gas for degassing liquid sulfur to carry out bubbling degassing on the liquid sulfur, and trace H dissolved in the liquid sulfur is removed2S and contains H2S and waste gas of liquid sulfur degassing of sulfur steam are extracted by a steam ejector, mixed with 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 a chimney 18 after being incinerated, so that the requirement of new environmental protection standards is met.
The following examples of the invention:
the de-iron scale-holding catalyst is preferably an LH-04 catalyst. The LH-04 catalytic protective agent is a catalytic protective agent which is developed by research institute of Qilu branch of China petrochemical and has the functions of removing iron and dirt and protecting a main catalyst. The LH-04 catalyst is honeycomb-shaped, has a proper pore channel structure, not only has the capability of removing large impurity particles, but also can deposit metal elements into the pore channel of the LH-04 catalyst, has good anti-coking performance and deferrization performance, and has higher activity, and the deferrization and scale-holding capacity can reach more than 30 percent;
the deoxygenation catalyst is preferably an LS-971 catalyst developed by the research institute of the British division of petrochemical companies. LS-971 catalyst is a high Claus activity and O-leakage removing catalyst2The protective bifunctional 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 any one-stage Claus reactor of the sulfur recovery device or be filled with other catalysts with different functions or types in a layered mode, and can generate a large amount of reaction heat in the process of removing oxygen leakage, so that the reaction temperature is increased, and the high temperature is favorable for the hydrolysis reaction of organic sulfur. Under the same device and the same process conditions, the total sulfur conversion rate can be improved by about 1 to 1.7 percent, and the method is particularly suitable for acid gas H2The sulfur recovery device with large S content or flow variation amplitude is used;
the organic sulfur hydrolysis catalyst is preferably an LS-981G catalyst developed by the research institute of the British division of petrochemical companies. LS-981G catalyst is TiO2The sulfur-based recovery catalyst has excellent organic sulfur hydrolysis activity. The catalyst has hydrolysis reaction on organic sulfide and H2S and SO2The Claus reaction has higher catalytic activity and reaches thermodynamic equilibrium nearly; for "O2Insensitivity to poisoning and resistance to hydrolysis reaction2"poisoning capacity of 0.2% (v), Claus reaction up to 1% (v) and once high concentrations of O have been excluded2The activity is almost completely restored; allowing a shorter contact time of about 3 seconds, corresponding to 1000h, for achieving the same conversion level-1-1200h-1Space velocity, 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 350m2Preferably LS-02 catalyst developed by the institute of Medium petrochemistry, Qilu division. The LS-02 catalyst is a novel alumina-based sulfur preparation catalyst with larger specific surface area and higher pore volume, which is developed on the basis of LS-300, and the catalyst 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; more reasonable pore structure, more macropores and bimodal distribution of pore structure, so that the sulfur generated by reaction can quickly leave the pore channel of the catalyst, and the Claus activity and the organic sulfur hydrolytic 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 research institute of the Qilu petrochemical division, the inlet temperature of a hydrogenation reactor using the catalyst can be controlled to be 220-260 ℃, the activity of the catalyst is improved by more than 30 percent compared with that of a common catalyst, the catalyst has excellent low-temperature hydrogenation and hydrolysis activity, and the content of organic sulfur in hydrogenation tail gas can be ensured to be lower than 20 ppm.
The catalyst of the invention can be purchased from the market, and the physicochemical properties and technical indexes of the catalyst are shown in the following table 1.
TABLE 1 physicochemical Properties and technical indices of the catalysts
Example 1
The process flow of the embodiment is shown in figure 1, and the process of the embodiment is applied to a sulfur recovery device which is a 40kt/a sulfur recovery device.
H2The acid gas with the S content of 65 percent is subjected to combustion reaction in the sulfur production furnace 1, the alkylated waste acid with the sulfuric acid content of 85 percent and the organic matter content of 15 percent is introduced into the sulfur production furnace and then subjected to high-temperature cracking reaction, natural gas is introduced as co-combustion gas to ensure the normal reaction of the acid gas and the complete cracking of the waste acid, and the temperature of the sulfur production furnace is controlled to 1050 ℃. The process gas at the outlet of the sulfur production furnace 1 enters a waste dust adsorber 3 (the operation temperature is 335 ℃, and an LH-04 catalytic protective agent is filled in the waste dust adsorber) after part of heat is recovered by a waste heat boiler 2, and the waste dust (the main component is ferric sulfate) in the waste dust adsorber is deposited in an inner pore channel of the catalyst; the process gas after absorbing and removing the waste dust is cooled by a primary sulfur cooler 4 to recover elemental sulfur, and then is reheated by a primary converter reheater 5 and enters a primary converter 6 (the catalyst grading scheme is that an LS-971 oxygen-removing catalyst with the height of 35 percent is filled at the upper part, an LS-981G organic sulfur hydrolysis catalyst with the height of 55 percent is filled at the middle part, and an LSH-03A low-temperature high-activity hydrogenation catalyst with the height of 10 percent is filled at the lower part), and in the primary converter 6, H in the process gas2S and SO2Claus reaction is generated to recover sulfur resource, organic sulfur in the process gas is hydrolyzed to generate hydrogen sulfide, and SO in the process gas3Is reduced to SO2(ii) a The process gas at the outlet of the primary converter 6 is recovered by a secondary sulfur cooler 7 to generate elemental sulfur, and the elemental sulfur is reheated by a secondary converter reheater 8 and then enters a secondary converter 9 (a catalyst grading scheme: LS-02 large specific surface area alumina-based sulfur recovery catalyst is completely filled) to continue to perform claus reaction to further recover sulfur resources; the process gas at the outlet of the secondary converter 9 passes through the tertiary sulfur cooler 10 to recover elemental sulfur and then obtain Claus tail gas; the Claus tail gas is reheated to 230 ℃ by a hydrogenation tail gas reheater 11, then enters a hydrogenation reactor 12, and under the action of a hydrogenation internal catalyst (LSH-03A) in the hydrogenation reactor 12, the sulfur-containing compounds are hydrogenated and converted into H2S, exchanging heat and condensing the generated hydrogenation tail gas through a hydrogenation tail gas heat exchanger 13, then cooling the hydrogenation tail gas in a quenching tower 14, allowing the cooled hydrogenation tail gas to enter an amine liquid absorption tower 15, and absorbing H in the hydrogenation tail gas by using amine liquid2S, generating purified tail gas; will partIntroducing the sub-purified tail gas into a liquid sulfur pool 16 as stripping gas for liquid sulfur degassing, and extracting waste gas from the liquid sulfur degassing and introducing the waste gas into a hydrogenation reactor 12 for treatment; the rest purified tail gas is introduced into an incinerator 17 to be incinerated and then is discharged through a chimney 18.
Through detection, the total sulfur conversion rate of the device in the embodiment is 97.11%, and the flue gas SO2Is 60mg/m3The iron content in the sulfur product is 0.0010 percent (m/m); the service life of the catalyst reaches more than 6 years.
Example 2
The process flow of the embodiment is shown in figure 1, and the process of the embodiment is applied to a sulfur recovery device, which is an 80kt/a sulfur recovery device.
H2The acid gas with the S content of 72 percent is subjected to combustion reaction in the sulfur production furnace 1, the alkylated waste acid with the sulfuric acid content of 90 percent and the organic matter content of 10 percent is introduced into the sulfur production furnace and then subjected to pyrolysis reaction, natural gas is introduced as co-combustion gas for ensuring the normal reaction of the acid gas and the complete pyrolysis of the waste acid, and the temperature of the sulfur production furnace is controlled to be 1220 ℃. The process gas at the outlet of the sulfur production furnace 1 enters a waste dust adsorber 3 (the operation temperature is 380 ℃, and an LH-04 catalytic protective agent is filled in the waste dust adsorber) after part of heat is recovered by a waste heat boiler 2, and the waste dust (the main component is ferric sulfate) in the waste dust adsorber is deposited in an inner pore channel of the catalyst; the process gas after absorbing and removing the waste dust is cooled by a primary sulfur cooler 4 to recover elemental sulfur, and then is reheated by a primary converter reheater 5 and enters a primary converter 6 (the catalyst grading scheme is that an LS-971 oxygen-removing catalyst with the height of 40 percent is filled at the upper part, an LS-981G organic sulfur hydrolysis catalyst with the height of 45 percent is filled at the middle part, and an LSH-03A low-temperature high-activity hydrogenation catalyst with the height of 15 percent is filled at the lower part), and in the primary converter 6, H in the process gas2S and SO2Claus reaction is generated to recover sulfur resource, organic sulfur in the process gas is hydrolyzed to generate hydrogen sulfide, and SO in the process gas3Is reduced to SO2(ii) a The process gas at the outlet of the primary converter 6 is recovered by a secondary sulfur cooler 7 to generate elemental sulfur, and is reheated by a secondary converter reheater 8 and then enters a secondary converter 9 (catalyst grading scheme: all the LS-02 alumina-based sulfur recovery catalysts with large specific surface area are filled) to continue to perform claus reaction to further recover sulfur resources(ii) a The process gas at the outlet of the secondary converter 9 passes through the tertiary sulfur cooler 10 to recover elemental sulfur and then obtain Claus tail gas; the Claus tail gas is reheated to 200 ℃ by a hydrogenation tail gas reheater 11, then enters a hydrogenation reactor 12, and under the action of a hydrogenation internal catalyst (LSH-03A) in the hydrogenation reactor 12, the sulfur-containing compounds are hydrogenated and converted into H2S, exchanging heat and condensing the generated hydrogenation tail gas through a hydrogenation tail gas heat exchanger 13, then cooling the hydrogenation tail gas in a quenching tower 14, allowing the cooled hydrogenation tail gas to enter an amine liquid absorption tower 15, and absorbing H in the hydrogenation tail gas by using amine liquid2S, generating purified tail gas; introducing part of the purified tail gas into a liquid sulfur pool 16 to be used as stripping gas for liquid sulfur degassing, and extracting waste gas from the liquid sulfur degassing and introducing the waste gas into a hydrogenation reactor 12 for treatment; the rest purified tail gas is introduced into an incinerator 17 to be incinerated and then is discharged through a chimney 18.
The detection proves that the total sulfur conversion rate of the device in the embodiment is 97.22%; flue gas SO2Is 45mg/m3(ii) a The iron content in the sulfur product is 0.0016 percent (m/m); the service life of the catalyst reaches more than 6 years.
Example 3
The process flow of the embodiment is shown in figure 1, and the process of the embodiment is applied to a sulfur recovery device, which is a 100kt/a sulfur recovery device.
H2The acid gas with 75 percent of S content is subjected to combustion reaction in the sulfur production furnace 1, the alkylated waste acid with 89 percent of sulfuric acid content and 11 percent of organic matters is introduced into the sulfur production furnace and then subjected to high-temperature cracking reaction, natural gas is introduced as co-combustion gas for ensuring the normal reaction of the acid gas and the complete cracking of the waste acid, and the temperature of the sulfur production furnace is controlled to 1350 ℃. The process gas at the outlet of the sulfur production furnace 1 enters a waste dust adsorber 3 (the operation temperature is 280 ℃, and an LH-04 catalytic protective agent is filled in the waste dust adsorber) after part of heat is recovered by a waste heat boiler 2, and the waste dust (the main component is ferric sulfate) in the waste dust adsorber is deposited in an inner pore channel of the catalyst; the process gas after absorbing and removing the waste dust is cooled by a primary sulfur cooler 4 to recover elemental sulfur, and then is reheated by a primary converter reheater 5 and enters a primary converter 6 (the catalyst grading scheme is that an LS-971 oxygen-removing catalyst with the height of 20 percent is filled at the upper part, an LS-981G organic sulfur hydrolysis catalyst with the height of 75 percent is filled at the middle part, and an LSH-03A low-temperature high-activity hydrogenation catalyst with the height of 5 percent is filled at the lower partAgent) in the primary reformer 6, H in the process gas2S and SO2Claus reaction is generated to recover sulfur resource, organic sulfur in the process gas is hydrolyzed to generate hydrogen sulfide, and SO in the process gas3Is reduced to SO2(ii) a The process gas at the outlet of the primary converter 6 is recovered by a secondary sulfur cooler 7 to generate elemental sulfur, and the elemental sulfur is reheated by a secondary converter reheater 8 and then enters a secondary converter 9 (a catalyst grading scheme: LS-02 large specific surface area alumina-based sulfur recovery catalyst is completely filled) to continue to perform claus reaction to further recover sulfur resources; the process gas at the outlet of the secondary converter 9 passes through the tertiary sulfur cooler 10 to recover elemental sulfur and then obtain Claus tail gas; the Claus tail gas is reheated to 280 ℃ by a hydrogenation tail gas reheater 11, then enters a hydrogenation reactor 12, and under the action of a hydrogenation internal catalyst (LSH-03A) in the hydrogenation reactor 12, the sulfur-containing compounds are hydrogenated and converted into H2S, exchanging heat and condensing the generated hydrogenation tail gas through a hydrogenation tail gas heat exchanger 13, then cooling the hydrogenation tail gas in a quenching tower 14, allowing the cooled hydrogenation tail gas to enter an amine liquid absorption tower 15, and absorbing H in the hydrogenation tail gas by using amine liquid2S, generating purified tail gas; introducing part of the purified tail gas into a liquid sulfur pool 16 to be used as stripping gas for liquid sulfur degassing, and extracting waste gas from the liquid sulfur degassing and introducing the waste gas into a hydrogenation reactor 12 for treatment; the rest purified tail gas is introduced into an incinerator 17 to be incinerated and then is discharged through a chimney 18.
The detection proves that the total sulfur conversion rate of the device in the embodiment is 97.18%; flue gas SO2Is 52mg/m3(ii) a The iron content in the sulfur product is 0.0018 percent (m/m); the service life of the catalyst reaches more than 6 years.
Example 4
The process flow of the embodiment is shown in figure 1, and the process of the embodiment is applied to a sulfur recovery device, which is a 70kt/a sulfur recovery device.
H2The acid gas with 82 percent of S content is subjected to combustion reaction in the sulfur production furnace 1, the alkylated waste acid with 90 percent of sulfuric acid content and 10 percent of organic matters is introduced into the sulfur production furnace and then subjected to pyrolysis reaction, natural gas is introduced as co-combustion gas for ensuring normal reaction of the acid gas and complete pyrolysis of the waste acid, and the temperature of the sulfur production furnace is controlled to 1400 ℃. Process gas channel at outlet of sulfur production furnace 1After recovering part of heat, the waste heat boiler 2 enters a waste dust adsorber 3 (the operation temperature is 350 ℃, and an LH-04 catalytic protective 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 an inner pore channel of the catalyst; the process gas after absorbing and removing the waste dust is cooled by a primary sulfur cooler 4 to recover elemental sulfur, and then is reheated by a primary converter reheater 5 and enters a primary converter 6 (the catalyst grading scheme is that an LS-971 oxygen-removing catalyst with the height of 30 percent is filled at the upper part, an LS-981G organic sulfur hydrolysis catalyst with the height of 60 percent is filled at the middle part, and an LSH-03A low-temperature high-activity hydrogenation catalyst with the height of 10 percent is filled at the lower part), and in the primary converter 6, H in the process gas2S and SO2Claus reaction is generated to recover sulfur resource, organic sulfur in the process gas is hydrolyzed to generate hydrogen sulfide, and SO in the process gas3Is reduced to SO2(ii) a The process gas at the outlet of the primary converter 6 is recovered by a secondary sulfur cooler 7 to generate elemental sulfur, and the elemental sulfur is reheated by a secondary converter reheater 8 and then enters a secondary converter 9 (a catalyst grading scheme: LS-02 large specific surface area alumina-based sulfur recovery catalyst is completely filled) to continue to perform claus reaction to further recover sulfur resources; the process gas at the outlet of the secondary converter 9 passes through the tertiary sulfur cooler 10 to recover elemental sulfur and then obtain Claus tail gas; the Claus tail gas is reheated to 220 ℃ by a hydrogenation tail gas reheater 11, then enters a hydrogenation reactor 12, and under the action of a hydrogenation internal catalyst (LSH-03A) in the hydrogenation reactor 12, the sulfur-containing compounds are hydrogenated and converted into H2S, exchanging heat and condensing the generated hydrogenation tail gas through a hydrogenation tail gas heat exchanger 13, then cooling the hydrogenation tail gas in a quenching tower 14, allowing the cooled hydrogenation tail gas to enter an amine liquid absorption tower 15, and absorbing H in the hydrogenation tail gas by using amine liquid2S, generating purified tail gas; introducing part of the purified tail gas into a liquid sulfur pool 16 to be used as stripping gas for liquid sulfur degassing, and extracting waste gas from the liquid sulfur degassing and introducing the waste gas into a hydrogenation reactor 12 for treatment; the rest purified tail gas is introduced into an incinerator 17 to be incinerated and then is discharged through a chimney 18.
The detection proves that the total sulfur conversion rate of the device in the embodiment is 97.16%; flue gas SO2Is 60mg/m3(ii) a The iron content in the sulfur product is 0.0021% (m/m); the service life of the catalyst reaches more than 6 years.
Example 5
The process flow of the embodiment is shown in figure 1, and the process of the embodiment is applied to a sulfur recovery device, which is an 80kt/a sulfur recovery device.
H2The acid gas with the S content of 55% undergoes a combustion reaction in the sulfur production furnace 1, the alkylated waste acid with the sulfuric acid content of 90% and the organic matter content of 10% is introduced into the sulfur production furnace and then undergoes a pyrolysis reaction, natural gas is introduced as co-combustion gas to ensure the normal reaction of the acid gas and the complete pyrolysis of the waste acid, and the temperature of the sulfur production furnace is controlled to 950 ℃. The process gas at the outlet of the sulfur production furnace 1 enters a waste dust adsorber 3 (the operation temperature is 320 ℃, and an LH-04 catalytic protective agent is filled in the waste dust adsorber) after part of heat is recovered by a waste heat boiler 2, and the waste dust (the main component is ferric sulfate) in the waste dust adsorber is deposited in an inner pore channel of the catalyst; the process gas after absorbing and removing the waste dust is cooled by a primary sulfur cooler 4 to recover elemental sulfur, and then is reheated by a primary converter reheater 5 and enters a primary converter 6 (the catalyst grading scheme is that an LS-971 oxygen-removing catalyst with the height of 35 percent is filled at the upper part, an LS-981G organic sulfur hydrolysis catalyst with the height of 55 percent is filled at the middle part, and an LSH-03A low-temperature high-activity hydrogenation catalyst with the height of 10 percent is filled at the lower part), and in the primary converter 6, H in the process gas2S and SO2Claus reaction is generated to recover sulfur resource, organic sulfur in the process gas is hydrolyzed to generate hydrogen sulfide, and SO in the process gas3Is reduced to SO2(ii) a The process gas at the outlet of the primary converter 6 is recovered by a secondary sulfur cooler 7 to generate elemental sulfur, and the elemental sulfur is reheated by a secondary converter reheater 8 and then enters a secondary converter 9 (a catalyst grading scheme: LS-02 large specific surface area alumina-based sulfur recovery catalyst is completely filled) to continue to perform claus reaction to further recover sulfur resources; the process gas at the outlet of the secondary converter 9 passes through the tertiary sulfur cooler 10 to recover elemental sulfur and then 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 under the action of a hydrogenation internal catalyst (LSH-03A) in the hydrogenation reactor 12, the sulfur-containing compounds are hydrogenated and converted into H2S, exchanging heat and condensing the generated hydrogenation tail gas through a hydrogenation tail gas heat exchanger 13, then cooling the hydrogenation tail gas in a quenching tower 14, allowing the cooled hydrogenation tail gas to enter an amine liquid absorption tower 15, and absorbing H in the hydrogenation tail gas by using amine liquid2S, generating purified tail gas; introducing part of the purified tail gas into a liquid sulfur pool 16 to be used as stripping gas for liquid sulfur degassing, and extracting waste gas from the liquid sulfur degassing and introducing the waste gas into a hydrogenation reactor 12 for treatment; the rest purified tail gas is introduced into an incinerator 17 to be incinerated and then is discharged through a chimney 18.
The detection proves that the total sulfur conversion rate of the device in the embodiment is 97.05 percent; flue gas SO2Is 82mg/m3(ii) a The iron content in the sulfur product is 0.0022 percent (m/m); the service life of the catalyst reaches more than 6 years.
Example 6
The process flow of the embodiment is shown in figure 1, and the process of the embodiment is applied to a sulfur recovery device, which is an 80kt/a sulfur recovery device.
H2The acid gas with the S content of 68 percent is subjected to combustion reaction in the sulfur production furnace 1, the alkylated waste acid with the sulfuric acid content of 88 percent and the organic matter content of 12 percent is introduced into the sulfur production furnace and then subjected to pyrolysis reaction, natural gas is introduced as co-combustion gas for ensuring the normal reaction of the acid gas and the complete pyrolysis of the waste acid, and the temperature of the sulfur production furnace is controlled to 1150 ℃. The process gas at the outlet of the sulfur production furnace 1 enters a waste dust adsorber 3 (the operation temperature is 360 ℃, and an LH-04 catalytic protective agent is filled in the waste dust adsorber) after part of heat is recovered by a waste heat boiler 2, and the waste dust (the main component is ferric sulfate) in the waste dust adsorber is deposited in an inner pore channel of the catalyst; the process gas after absorbing and removing the waste dust is cooled by a primary sulfur cooler 4 to recover elemental sulfur, and then is reheated by a primary converter reheater 5 and enters a primary converter 6 (the catalyst grading scheme is that an LS-971 oxygen-removing catalyst with the height of 23 percent is filled at the upper part, an LS-981G organic sulfur hydrolysis catalyst with the height of 62 percent is filled at the middle part, and an LSH-03A low-temperature high-activity hydrogenation catalyst with the height of 15 percent is filled at the lower part), and in the primary converter 6, H in the process gas2S and SO2Claus reaction is generated to recover sulfur resource, organic sulfur in the process gas is hydrolyzed to generate hydrogen sulfide, and SO in the process gas3Is reduced to SO2(ii) a The process gas at the outlet of the primary converter 6 is recovered by a secondary sulfur cooler 7 to generate elemental sulfur, and is reheated by a secondary converter reheater 8 and then enters a secondary converter 9 (catalyst grading scheme: all the LS-02 alumina-based sulfur recovery catalysts with large specific surface area) to continuously generate clausThe sulfur resource is further recovered by the reaction; the process gas at the outlet of the secondary converter 9 passes through the tertiary sulfur cooler 10 to recover elemental sulfur and then obtain Claus tail gas; the Claus tail gas is reheated to 250 ℃ by a hydrogenation tail gas reheater 11, then enters a hydrogenation reactor 12, and under the action of a hydrogenation internal catalyst (LSH-03A) in the hydrogenation reactor 12, the sulfur-containing compounds are hydrogenated and converted into H2S, exchanging heat and condensing the generated hydrogenation tail gas through a hydrogenation tail gas heat exchanger 13, then cooling the hydrogenation tail gas in a quenching tower 14, allowing the cooled hydrogenation tail gas to enter an amine liquid absorption tower 15, and absorbing H in the hydrogenation tail gas by using amine liquid2S, generating purified tail gas; introducing part of the purified tail gas into a liquid sulfur pool 16 to be used as stripping gas for liquid sulfur degassing, and extracting waste gas from the liquid sulfur degassing and introducing the waste gas into a hydrogenation reactor 12 for treatment; the rest purified tail gas is introduced into an incinerator 17 to be incinerated and then is discharged through a chimney 18.
The detection shows that the total sulfur conversion rate of the device in the embodiment is 97.02%; flue gas SO2Is 72mg/m3(ii) a The iron content in the sulfur product is 0.0025% (m/m); the service life of the catalyst reaches 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 dust adsorber 3 is not provided.
After the device of the comparative example operates for a period of time, the pressure drop of the reactor bed layer is greatly increased, the iron content in the produced sulfur reaches 0.08% (m/m), and the sulfur cannot be smoothly delivered from a factory. The operation is continued, the pressure drop of the bed layer is continuously increased, the device is forced to be stopped, and the discharged catalyst bed is fully accumulated with light pink waste dust.
Comparative example 2
The process flow of this comparative example is shown in fig. 1, and the system configuration and process flow are the same as those of example 1, and the difference is only that the catalyst grading scheme is as follows: in the first-stage converter 6, 35% of LS-971 oxygen-removing catalyst is filled at the upper part, and 65% of LS-981G catalyst is filled at the lower part; the secondary converter 9 is fully loaded with LS-02 catalyst.
The total sulfur conversion for the apparatus of this comparative example was 96.28%; flue gas SO2Is 179mg/m3(ii) a The sulfur product contains iron0.0026% (m/m); a part of SO is generated by cracking waste acid3The part of SO3The device can not be processed, so that the device is seriously corroded, and the device is forced to be shut down after being operated for 6 months.
Comparative example 3
The process flow of this comparative example is shown in fig. 1, and the system configuration and process flow are the same as those of example 1, and the difference is only that the catalyst grading scheme is as follows: in the first-stage converter 6, 35% of LS-02 catalyst is filled at the upper part, and 65% of LS-981G catalyst is filled at the lower part; the secondary reformer 9 is fully loaded with LS-02 catalyst.
The total sulfur conversion for the apparatus of this comparative example was 95.56%; flue gas SO2Is 226mg/m3(ii) a The iron content in the sulfur product is 0.0017 percent (m/m); because the catalyst of the device is seriously sulfated, the catalyst is forced to be replaced after being used for three years.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. A system for efficiently treating alkylated waste acid to prepare sulfur is characterized by comprising a thermal reaction unit, a catalytic reaction unit and a tail gas purification unit which are sequentially connected; wherein,
the thermal reaction unit includes:
a sulfur production furnace (1), the waste alkylated acid to be treated and H-containing2The acid gas of S reacts in the sulfur production furnace (1) to generate process gas containing elemental sulfur;
a waste dust adsorber (3), wherein a de-iron scale-containing catalyst is filled in the waste dust adsorber (3) and is used for adsorbing iron-containing waste dust in the process gas;
the process gas after adsorption treatment enters the sulfur cooler for condensation, the sulfur 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 a oxygen-leakage-removing catalyst, an organic sulfur hydrolysis catalyst and a hydrogenation catalyst, and the process gas can simultaneously carry out Claus reaction, organic sulfur hydrolysis reaction and SO3Carrying out reduction reaction to obtain elemental sulfur and catalytic tail gas;
a secondary converter (9), wherein a sulfur recovery catalyst is filled in the secondary converter (9), and the catalytic tail gas is subjected to Claus catalytic conversion to obtain elemental sulfur and Claus tail gas;
the tail gas purifying unit comprises:
a hydrogenation reactor (12) in which said Claus tail gas hydrogenates sulfur-containing compounds to H in said hydrogenation reactor (12)2S, obtaining a product containing H2Hydrogenation tail gas of S;
an absorption tower (15), wherein the absorption tower (15) is used for absorbing H in the hydrogenation tail gas2S, obtaining purified tail gas;
and the tail gas incinerator (17) is used for incinerating and discharging the purified tail gas.
2. The system for efficiently processing alkylated waste acid to prepare sulfur according to claim 1, wherein a waste heat boiler (2) is further arranged between the sulfur production furnace (1) and the waste dust adsorber (3) and is used for recovering part of heat.
3. The system for efficiently processing alkylated waste acid to prepare sulfur according to claim 1 or 2, wherein in the primary converter (6), the oxygen-removing catalyst is loaded at the top position, the organic sulfur hydrolysis catalyst is loaded at the middle position, and the hydrogenation catalyst is loaded at the bottom position.
4. The system for efficiently treating alkylated waste acid to prepare sulfur according to claim 3, wherein: in the first-stage converter (6), the upper part is filled with 20-40% of high-grade oxygen-removing catalyst, the middle part is filled with 45-75% of high-grade organic sulfur hydrolysis catalyst, and the lower part is filled with 5-15% of high-grade low-temperature high-activity hydrogenation catalyst.
5. The system for efficiently processing alkylated waste acid to prepare sulfur according to any one of claims 1 to 4, wherein the first converter (6) and the second converter (9) are respectively followed by the sulfur cooler.
6. The system for efficiently processing alkylated waste acid to prepare sulfur according to any one of claims 1 to 5, wherein the first converter (6) and the second converter (9) are respectively provided with a primary converter reheater (5) and a secondary converter reheater (8).
7. A process for efficiently treating alkylated waste acid to prepare sulfur based on the system of any one of claims 1 to 6, wherein the process comprises the following steps:
(1) will contain H2The acid gas of S and the alkylation waste acid to be treated are led into the sulfur production furnace (1), and the H is contained2The acid gas of S is partially combusted in the sulfur production furnace (1) and converted into SO2The alkylated waste acid undergoes pyrolysis to generate SO2And a small amount of SO3(ii) a Obtained H2S and SO2A Claus reaction takes place to generate a process gas containing elemental sulphur; inputting the process gas into the waste dust absorber (3), and removing waste dust of the process gas through catalysis; the process gas after adsorption treatment enters the sulfur cooler and is condensed to obtain liquid sulfur which is collected, and the process gas after liquid sulfur collection continues to enter the catalytic reaction unit;
(2) the process gas enters the first converter (6) and is subjected to a Claus reaction, an organic sulphur hydrolysis reaction and SO simultaneously under the action of a selected catalyst3Carrying out reduction reaction to obtain elemental sulfur and catalytic tail gas; collecting elemental sulfur and continuing to enter the obtained catalytic tail gas into the second converter (9), performing Claus catalytic conversion under the action of a selected catalyst to generate elemental sulfur and Claus tail gas, collecting elemental sulfur, and allowing the Claus tail gas to enterEntering the tail gas purification unit;
(3) the Claus tail gas is subjected to hydrogenation catalytic reaction in the hydrogenation reactor (12) to convert sulfur-containing compounds in the Claus tail gas into H2S, and enters an absorption tower (15) to absorb H2S; the purified tail gas is introduced into the tail gas incinerator (15) and is exhausted after incineration.
8. The process for preparing sulfur by efficiently treating alkylated waste acid according to claim 7, wherein the step (1) further comprises the step of introducing natural gas as a secondary combustion gas into the sulfur production furnace (1).
9. The process for preparing sulfur by efficiently treating alkylated waste acid according to claim 7 or 8, wherein the step (2) further comprises the step of condensing the obtained elemental sulfur and tail gas in a sulfur cooler after the catalytic reaction of the primary converter (6) and the secondary converter (9), and collecting liquid sulfur.
10. The process for preparing sulfur by efficiently processing alkylated waste acid according to any one of claims 7 to 9, 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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