CN110092358A - A kind of processing method of waste sulfuric acid from alkylation - Google Patents
A kind of processing method of waste sulfuric acid from alkylation Download PDFInfo
- Publication number
- CN110092358A CN110092358A CN201910440175.7A CN201910440175A CN110092358A CN 110092358 A CN110092358 A CN 110092358A CN 201910440175 A CN201910440175 A CN 201910440175A CN 110092358 A CN110092358 A CN 110092358A
- Authority
- CN
- China
- Prior art keywords
- sulfuric acid
- alkylation
- solvent
- waste sulfuric
- processing method
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 128
- 239000002699 waste material Substances 0.000 title claims abstract description 50
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 47
- 230000029936 alkylation Effects 0.000 title claims abstract description 46
- 238000003672 processing method Methods 0.000 title claims abstract description 20
- 239000002904 solvent Substances 0.000 claims abstract description 43
- 239000007788 liquid Substances 0.000 claims abstract description 37
- 239000002608 ionic liquid Substances 0.000 claims abstract description 20
- 238000000926 separation method Methods 0.000 claims abstract description 19
- -1 alkyl imidazolium cation Chemical compound 0.000 claims description 50
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 35
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 claims description 20
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 18
- 150000003839 salts Chemical class 0.000 claims description 14
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 12
- 239000001282 iso-butane Substances 0.000 claims description 10
- 235000013847 iso-butane Nutrition 0.000 claims description 10
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 claims description 8
- 150000001768 cations Chemical class 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 7
- 239000006228 supernatant Substances 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 5
- ZXMGHDIOOHOAAE-UHFFFAOYSA-N 1,1,1-trifluoro-n-(trifluoromethylsulfonyl)methanesulfonamide Chemical compound FC(F)(F)S(=O)(=O)NS(=O)(=O)C(F)(F)F ZXMGHDIOOHOAAE-UHFFFAOYSA-N 0.000 claims description 4
- WGVGZVWOOMIJRK-UHFFFAOYSA-N 1-hexyl-3-methyl-2h-imidazole Chemical compound CCCCCCN1CN(C)C=C1 WGVGZVWOOMIJRK-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 claims description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical group C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 4
- BQJCRHHNABKAKU-KBQPJGBKSA-N morphine Chemical compound O([C@H]1[C@H](C=C[C@H]23)O)C4=C5[C@@]12CCN(C)[C@@H]3CC5=CC=C4O BQJCRHHNABKAKU-KBQPJGBKSA-N 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- KTUWFYALZIAAGE-UHFFFAOYSA-N 1-methyl-3-octyl-2h-imidazole Chemical compound CCCCCCCCN1CN(C)C=C1 KTUWFYALZIAAGE-UHFFFAOYSA-N 0.000 claims description 3
- 150000001450 anions Chemical class 0.000 claims description 3
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 claims description 2
- RVEJOWGVUQQIIZ-UHFFFAOYSA-N 1-hexyl-3-methylimidazolium Chemical compound CCCCCCN1C=C[N+](C)=C1 RVEJOWGVUQQIIZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- 229960005181 morphine Drugs 0.000 claims description 2
- 239000001294 propane Substances 0.000 claims description 2
- 150000003217 pyrazoles Chemical class 0.000 claims description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- 125000002029 aromatic hydrocarbon group Chemical group 0.000 claims 2
- 125000000963 oxybis(methylene) group Chemical group [H]C([H])(*)OC([H])([H])* 0.000 claims 2
- 206010011224 Cough Diseases 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
- 125000001033 ether group Chemical group 0.000 claims 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- IJDNQMDRQITEOD-UHFFFAOYSA-N sec-butylidene Natural products CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 claims 1
- 125000003944 tolyl group Chemical group 0.000 claims 1
- 125000001889 triflyl group Chemical group FC(F)(F)S(*)(=O)=O 0.000 claims 1
- 238000005265 energy consumption Methods 0.000 abstract description 4
- 230000008929 regeneration Effects 0.000 abstract description 3
- 238000011069 regeneration method Methods 0.000 abstract description 3
- 239000002253 acid Substances 0.000 description 36
- 239000004215 Carbon black (E152) Substances 0.000 description 23
- 229930195733 hydrocarbon Natural products 0.000 description 23
- 150000002430 hydrocarbons Chemical class 0.000 description 23
- 238000000605 extraction Methods 0.000 description 19
- 238000000034 method Methods 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 6
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 5
- 238000005336 cracking Methods 0.000 description 4
- 239000000284 extract Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005292 vacuum distillation Methods 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- 125000000217 alkyl group Chemical group 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
- 239000003054 catalyst Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 150000001993 dienes Chemical class 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000003337 fertilizer Substances 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 125000001280 n-hexyl group Chemical group C(CCCCC)* 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 description 1
- WXMVWUBWIHZLMQ-UHFFFAOYSA-N 3-methyl-1-octylimidazolium Chemical compound CCCCCCCCN1C=C[N+](C)=C1 WXMVWUBWIHZLMQ-UHFFFAOYSA-N 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 150000001350 alkyl halides Chemical class 0.000 description 1
- 239000013556 antirust agent Substances 0.000 description 1
- XTKDAFGWCDAMPY-UHFFFAOYSA-N azaperone Chemical compound C1=CC(F)=CC=C1C(=O)CCCN1CCN(C=2N=CC=CC=2)CC1 XTKDAFGWCDAMPY-UHFFFAOYSA-N 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000006206 glycosylation reaction Methods 0.000 description 1
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 150000003233 pyrroles Chemical class 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000013076 target substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- C01B17/69—Sulfur trioxide; Sulfuric acid
- C01B17/90—Separation; Purification
- C01B17/92—Recovery from acid tar or the like, e.g. alkylation acids
- C01B17/925—Recovery from acid tar or the like, e.g. alkylation acids by processes involving a liquid-liquid extraction
-
- 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
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of processing methods of waste sulfuric acid from alkylation.The processing method of waste sulfuric acid from alkylation disclosed by the invention is the following steps are included: waste sulfuric acid from alkylation, solvent and ionic liquid are mixed, liquid separation.The processing method of waste sulfuric acid from alkylation of the invention is at low cost, less energy consumption, pollution are small, it can be achieved that Waste Sulfuric Acid regeneration.
Description
Technical field
The present invention relates to a kind of processing methods of waste sulfuric acid from alkylation.
Background technique
Alkylate oil can meet the gasoline blend component of cleaning and high-octane rating requirement simultaneously, and alkylation process is to the world
Oil product upgrading is significant.Catalyst of the sulfuric acid in reaction zone as alkylated reaction, theoretically, catalyst promote chemistry anti-
It answers and itself should not change.But actually due to the influence of the impurity in side reaction and raw material, sour concentration will gradually be dropped
Low, a part of acid will be consumed.Optimum acid concentration is probably in 89%-96%, alkylation per ton in sulfuric acid alkylation plant
The acid consumption of oil is about between 77-102Kg, then the device of an annual output 100Kt alkylate oil, will consume nearly 10Kt's in 1 year
Sulfuric acid, and generate almost same amount of spent acid.
Waste sulfuric acid from alkylation is a kind of biggish dark red colloidal liquid of viscosity, and ingredient is mainly free sulfuric acid, high score
Sub- alkene, alkadienes, alkyl sulfonic acid, alkylsurfuric acid and dissolution sulfide (hydrogen sulfide, mercaptan etc.) therein, property are unstable
It is fixed, can constantly be oxidized in air, after and the reactions such as olefinic polymerization oxidation can occur, give out off-odor.Largely
Spent acid is difficult to handle, it will greatly threatens environment composition.
Currently, the first is by alkyl sulfur both at home and abroad there are mainly three types of industrialized waste sulfuric acid from alkylation treatment process
Acid is used to produce ammonium sulfate, fertilizer etc. after concentrating.The ammonium sulfate color that such technical matters is produced is deeper, irritant gas
Body generates.Organic matter in the Waste Sulfuric Acid of part enters crops by fertilizer, further endangers human health.Second is to utilize
It is alkylated spent acid production white carbon black and petroleum antirust agent.This method wastewater discharge is big, and the added value of product of generation is low.The third is
Using high-temperature cracking method, alkylation spent acid is made to be cracked into SO2And H2O, organic cracking is at CO2And H2O, then gas again into
Enter regeneration of sulfuric acid device, generates technical grade sulfuric acid.Such method and process is mature, but energy consumption is high for cracking sulfuric acid at high temperature, to setting
Standby corrosion is more serious, causes this kind of processing method operating cost high, system investments are big.
Summary of the invention
The technical problem to be solved by the present invention is in order to overcome in the prior art waste sulfuric acid from alkylation processing method it is few
Defect, and provide a kind of processing method of waste sulfuric acid from alkylation.This method is at low cost, less energy consumption, pollution are small, it can be achieved that sulfur waste
The regeneration of acid.
The present invention mainly solves above-mentioned technical problem by the following technical programs.
The present invention provides a kind of processing methods of waste sulfuric acid from alkylation comprising following steps: by waste sulfuric acid from alkylation,
Solvent and ionic liquid mixing, liquid separation.
The solvent can be conventional for this field, and specifically preferred according to the invention is alkane solvents, aromatic hydrocarbon solvent, alkyl halide
One of hydrocarbon solvent and ether solvent are a variety of, further preferably alkane solvents, aromatic hydrocarbon solvent and halogenated alkane
One of class solvent is a variety of.The alkane solvents can be conventional for this field, and specifically preferred according to the invention is propane, positive fourth
One of alkane, iso-butane and n-hexane are a variety of, further preferably iso-butane.The aromatic hydrocarbon solvent can be this field
Conventional, specifically preferred according to the invention is benzene and/or toluene, further preferably toluene.The halogenated alkanes solvents can be this
Field is conventional, specifically preferred according to the invention for one of methylene chloride, chloroform and carbon tetrachloride or a variety of.The ether solvent
Can be conventional for this field, specifically preferred according to the invention is tetrahydrofuran.
Cation in the ionic liquid be preferably alkyl imidazolium cation, pyrazoles cationoid, pyridine cationoid,
One of pyrroles's cationoid, morphine cationoid, quaternaries cation and quaternary alkylphosphonium salt cationoid are a variety of, further
Preferably alkyl imidazolium cation.
The alkyl imidazolium cation can be conventional for this field, and the present invention is preferably 1-C1~C10Alkyl -3-C1~C10Alkane
Base glyoxaline cation, further preferably 1-C4~C8Alkyl -3-C1~C4Alkylimidazolium cation is still more preferably 1-
One in butyl -3- methyl imidazolium cation, 1- hexyl -3- methyl imidazolium cation and 1- octyl -3- methyl imidazolium cation
Kind is a variety of.
Anion in the ionic liquid is preferably Br-、Cl-、BF4 -、PF6 -、NTf2 -、C(CN)3 -、N(CN)2 -With
[CH3(C2H4O)2SO4]-(i.e.) one of or a variety of, further preferably PF6 -、BF4 -With
NTf2 -One of or it is a variety of.
The ionic liquid is preferably 1- butyl -3- methylimidazole hexafluorophosphate, 1- hexyl -3- methylimidazole hexafluoro
Phosphate, 1- octyl -3- methylimidazole hexafluorophosphate, 1- butyl -3- methyl imidazolium tetrafluoroborate, 1- hexyl -3- methyl
Tetrafluoroborate, 1- octyl -3- methyl imidazolium tetrafluoroborate, 1- butyl -3- methylimidazole bis-trifluoromethylsulfoandimide
In salt, 1- hexyl -3- methylimidazole bis-trifluoromethylsulfoandimide salt and 1- octyl -3- methylimidazole bis-trifluoromethylsulfoandimide salt
One or more, further preferably 1- butyl -3- methylimidazole bis-trifluoromethylsulfoandimide salt, 1- butyl -3- methyl miaow
One of azoles hexafluorophosphate, 1- butyl -3- methylimidazole hexafluorophosphate and 1- hexyl -3- methyl imidazolium tetrafluoroborate
Or it is a variety of.
The mass ratio of the solvent and the waste sulfuric acid from alkylation is preferably 0.1:1~15:1, further preferably
0.5:1~10:1 is still more preferably 2:1~10:1 (such as 2:1,5:1 and 10:1).
The mass ratio of the ionic liquid and the waste sulfuric acid from alkylation is preferably 0.1:1~5:1, further preferably
For 0.4:1~2:1, further preferably 1:1~2:1 (such as 1:1 and 2:1).
The mixed mode can be conventional for this field, specifically preferred according to the invention for stirring, further preferably machinery
Stirring.The churned mechanically revolving speed is preferably 100~2000r/min, further preferably 500~1500r/min (such as
500r/min, 1000r/min and 1500r/min).
The mixed temperature can be conventional for this field, and specifically preferred according to the invention is 0~80 DEG C, further preferably 5
~60 DEG C, be still more preferably 10~30 DEG C (such as 25 DEG C and 30 DEG C).
The mixed time can be conventional for this field, specifically preferred according to the invention for more than or equal to 5 minutes, further excellent
Be selected as 5 minutes~3 hours, still more preferably for 0.5~3 hour (such as 0.5 hour, 0.75 hour, 1 hour, 1.5 hours,
3 hours).
The mixed pressure can be conventional for this field, and specifically preferred according to the invention is 0.1~2MPa, further preferably
0.1~0.4MPa (such as 0.1MPa and 0.4MPa).
The mode of the liquid separation can be conventional for this field, specifically preferred according to the invention to stand or being centrifuged, further preferably
For centrifugation.
The temperature of the liquid separation can be conventional for this field, those skilled in the art can by the solvent type into
Row adjustment, specifically preferred according to the invention is 0~80 DEG C, and further preferably 5~60 DEG C, be still more preferably 10~30 DEG C of (examples
Such as 25 DEG C).
It can also further comprise the recycling of ionic liquid after the liquid separation.The mode of the recycling is preferably by liquid separation
The supernatant liquid obtained afterwards is evaporated under reduced pressure.
In the present invention, the waste sulfuric acid from alkylation is preferably that alkylated reaction occurs in concentrated sulfuric acid for butylene and iso-butane
Generated Waste Sulfuric Acid.The waste sulfuric acid from alkylation is preferably the waste sulfuric acid from alkylation from the Zhejiang match chromium energy.
In actual alkyl chemical industry, black sulfuric acid and fresh sulfuric acid (mass concentration 98%-99%) enter alkane together
In glycosylation reaction device, the molten hydrocarbon of acid of remaining height ionization is diluted, and just be can be used as proton transfer medium, is promoted alkyl
Change the generation of main reaction.
Without prejudice to the field on the basis of common sense, above-mentioned each optimum condition, can any combination to get the present invention it is each preferably
Example.
The reagents and materials used in the present invention are commercially available.
The positive effect of the present invention is that: the present invention extracts the molten hydrocarbon of acid in waste sulfuric acid from alkylation using extraction,
Mechanical stirring comes into full contact with Waste Sulfuric Acid and organic solvent, and the impurity in spent acid is dissolved in solvent.Compared with high-temperature cracking method,
Apparatus cost is small, and low energy consumption, is that can carry out industrialized method.Select ionic liquid as extraction process extractant,
Its physicochemical properties changes with the variation of ionic liquid zwitterion type and substituent group, has very extensive dissolution energy
Power and for target substance have can modulation soluble end, dissolubility of the molten hydrocarbon of acid in extractant can be enhanced.Ion simultaneously
Liquid has lower saturated vapor pressure and more stable thermodynamic property, can recycle in extraction process, reduces loss,
And then it reduces environmental pollution.
Specific embodiment
The present invention is further illustrated below by the mode of embodiment, but does not therefore limit the present invention to the reality
It applies among a range.In the following examples, the experimental methods for specific conditions are not specified, according to conventional methods and conditions, or according to quotient
The selection of product specification.
What the molten hydrocarbon of acid was primarily referred to as being formed in alkylated reaction in the present invention contains a large amount of double bond conjugated dienes, C5Ring
And its hydrocarbon polymer (the C of branched chain compound12-C20)。
Extraction efficiency=[(C in the present invention0-Cf)/C0] * 100%, wherein C0Refer to extracting the molten hydrocarbon of acid in preceding spent acid
Concentration;CfFor the concentration of the molten hydrocarbon of acid in spent acid after extraction.The volume of spent acid and spent acid after extraction is basically unchanged before extracting.The present invention
Waste sulfuric acid from alkylation refers to that butylene and iso-butane are alkylated in concentrated sulfuric acid in following Examples 1 to 4 and comparative example 1
Waste Sulfuric Acid caused by reacting, waste sulfuric acid from alkylation of the Waste Sulfuric Acid from the Zhejiang match chromium energy.Utilize ultraviolet specrophotometer
The absorbance for measuring the organic compound containing conjugated double bond structures carries out quantitative analysis to the molten hydrocarbon component content of acid.
Embodiment 1
Conical flask is added in the 1- butyl -3- methylimidazole hexafluorophosphate of 10g waste sulfuric acid from alkylation, 20g toluene, 10g
In 250mL, 1h is mixed under conditions of 25 DEG C, 0.1MPa, power of agitator 1000r/min.It is mixed by what is obtained after stirring
Liquid pouring is closed in centrifuge tube, carries out Liquid liquid Separation using centrifuge at 25 DEG C.After the completion of centrifugation, supernatant liquid is containing quilt
Extract the extraction phase of the molten hydrocarbon of object acid, toluene and 1- butyl -3- methylimidazole hexafluorophosphate, lower layer is black sulfuric acid extracted
Phase.Toluene and the molten hydrocarbon of acid can be separated through vacuum distillation, toluene and 1- butyl -3- methylimidazole hexafluorophosphate can be recycled.
The single extraction efficiency of the molten hydrocarbon of acid is 81.2%.
Embodiment 2
By 10g waste sulfuric acid from alkylation, 50g methylene chloride, 10g (1- butyl -3- methylimidazole hexafluorophosphate and 1- oneself
Base -3- methyl imidazolium tetrafluoroborate) (wherein 1- butyl -3- methylimidazole hexafluorophosphate and 1- hexyl -3- methylimidazole four
The molar ratio of borofluoride is 1:1) it is added in conical flask 250mL, under conditions of 30 DEG C, 0.1MPa, power of agitator 500r/min
1.5h is mixed.After stirring, obtained mixed liquor is stood at 25 DEG C and carries out Liquid liquid Separation.Supernatant liquid is containing quilt
Extract the molten hydrocarbon of object acid, methylene chloride, 1- butyl -3- methylimidazole hexafluorophosphate and 1- hexyl -3- methyl imidazolium tetrafluoroborate
Extraction phase, lower layer be black sulfuric acid phase extracted.Methylene chloride and the molten hydrocarbon of acid can be separated by being evaporated under reduced pressure, methylene chloride,
1- butyl -3- methylimidazole hexafluorophosphate and 1- hexyl -3- methyl imidazolium tetrafluoroborate can be recycled.The list of the molten hydrocarbon of acid
Secondary extraction efficiency is 86.1%.
Embodiment 3
By 5g waste sulfuric acid from alkylation, 50g iso-butane, 5g (1- butyl -3- methylimidazole bis-trifluoromethylsulfoandimide salt and
1- butyl -3- methylimidazole hexafluorophosphate) (wherein 1- butyl -3- methylimidazole bis-trifluoromethylsulfoandimide salt and 1- butyl -
The molar ratio of 3- methylimidazole hexafluorophosphate is 1:1) it is added in conical flask 250mL, 25 DEG C, 0.4MPa, power of agitator
0.5h is mixed under conditions of 1500r/min.After stirring, obtained mixing liquid is poured in centrifuge tube, 25
Liquid liquid Separation is carried out using centrifuge at DEG C.After the completion of centrifugation, supernatant liquid is containing by the molten hydrocarbon of extraction object acid, iso-butane, 1- butyl-
The extraction phase of 3- methylimidazole bis-trifluoromethylsulfoandimide salt and 1- butyl -3- methylimidazole hexafluorophosphate, lower layer are extraction
Black sulfuric acid phase afterwards.1- butyl -3- methylimidazole bis-trifluoromethylsulfoandimide salt and 1- butyl -3- can be separated through vacuum distillation
Methylimidazole hexafluorophosphate and the molten hydrocarbon of acid, 1- butyl -3- methylimidazole bis-trifluoromethylsulfoandimide salt and 1- butyl -3- methyl
Limidazolium hexafluorophosphate can be recycled.The single extraction efficiency of the molten hydrocarbon of acid is 88.8%.
Embodiment 4
By 5g waste sulfuric acid from alkylation, 25g iso-butane, 5g (1- butyl -3- methylimidazole hexafluorophosphate and 1- hexyl -
3- methyl imidazolium tetrafluoroborate) (wherein 1- butyl -3- methylimidazole hexafluorophosphate and 1- hexyl -3- methylimidazole tetrafluoro
The molar ratio of borate is 1:1) it is added in conical flask 250mL, 30 DEG C, it is mixed under conditions of 0.4MPa, 1000r/min.
After stirring, obtained mixing liquid is poured in centrifuge tube, carries out Liquid liquid Separation using centrifuge.After the completion of centrifugation,
Supernatant liquid is containing by the molten hydrocarbon of extraction object acid, iso-butane, 1- butyl -3- methylimidazole hexafluorophosphate and 1- hexyl -3- methyl miaow
The extraction phase of azoles tetrafluoroborate, lower layer are black sulfuric acid phase extracted.1- butyl -3- methyl miaow can be separated through vacuum distillation
Azoles hexafluorophosphate and 1- hexyl -3- methyl imidazolium tetrafluoroborate and the molten hydrocarbon of acid, 1- butyl -3- methylimidazole hexafluorophosphate
It can be recycled with 1- hexyl -3- methyl imidazolium tetrafluoroborate.The single extraction efficiency of the molten hydrocarbon of acid is as shown in table 1.
The single extraction efficiency of the molten hydrocarbon of acid under the different extraction times of table 1
Comparative example 1
10g waste sulfuric acid from alkylation and 20g toluene are added in 250mL conical flask, 25 DEG C, 0.1MPa, power of agitator
1h is mixed under conditions of 1000r/min.After stirring, obtained mixing liquid is poured in centrifuge tube, at 25 DEG C
It is lower to carry out Liquid liquid Separation using centrifuge.After the completion of centrifugation, supernatant liquid is toluene phase, and lower layer is sulfuric acid phase extracted.It should
The toluene that process obtains mutually without apparent color change, does not contain the chromatographic peak of the molten hydrocarbon of acid mutually through gas chromatographic analysis toluene.
Claims (10)
1. a kind of processing method of waste sulfuric acid from alkylation, which is characterized in that it is the following steps are included: by waste sulfuric acid from alkylation, molten
Agent and ionic liquid mixing, liquid separation.
2. the processing method of waste sulfuric acid from alkylation as described in claim 1, which is characterized in that
The solvent is one of alkane solvents, aromatic hydrocarbon solvent, halogenated alkanes solvents and ether solvent or a variety of;
And/or the cation in the ionic liquid is alkyl imidazolium cation, pyrazoles cationoid, pyridine cationoid, pyrrole
Cough up one of cationoid, morphine cationoid, quaternaries cation and quaternary alkylphosphonium salt cationoid or a variety of;
And/or the anion in the ionic liquid is Br-、Cl-、BF4 -、PF6 -、NTf2 -、C(CN)3 -、N(CN)2 -[CH3
(C2H4O)2SO4]-One of or it is a variety of;
And/or the mass ratio of the solvent and the waste sulfuric acid from alkylation is 0.1:1~15:1;
And/or the mass ratio of the ionic liquid and the waste sulfuric acid from alkylation is 0.1:1~5:1;
And/or the mixed mode is stirring;
And/or the mixed temperature is 0~80 DEG C;
And/or the mixed time is more than or equal to 5 minutes;
And/or the mixed pressure is 0.1~2MPa;
And/or the mode of the liquid separation is to stand or be centrifuged;
And/or the temperature of the liquid separation is 0~80 DEG C.
3. the processing method of waste sulfuric acid from alkylation as claimed in claim 2, which is characterized in that
When the solvent is alkane solvents, the solvent is one of propane, normal butane, iso-butane and n-hexane
Or it is a variety of;
And/or when the solvent is aromatic hydrocarbon solvent, the solvent is benzene and/or toluene;
And/or when the solvent is halogenated alkanes solvents, the solvent is methylene chloride, chloroform and carbon tetrachloride
One of or it is a variety of;
And/or when the solvent is ether solvent, the solvent is tetrahydrofuran;
And/or the cation in the ionic liquid is alkyl imidazolium cation;
And/or the anion in the ionic liquid is PF6 -、BF4 -And NTf2 -One of or it is a variety of;
And/or the mass ratio of the solvent and the waste sulfuric acid from alkylation is 0.5:1~10:1;
And/or the mass ratio of the ionic liquid and the waste sulfuric acid from alkylation is 0.4:1~2:1;
And/or the mixed mode is mechanical stirring;
And/or the mixed temperature is 5~60 DEG C;
And/or the mixed time is 5 minutes~3 hours;
And/or the mixed pressure is 0.1~0.4MPa;
And/or the mode of the liquid separation is centrifugation;
And/or the temperature of the liquid separation is 5~60 DEG C.
4. the processing method of waste sulfuric acid from alkylation as claimed in claim 3, which is characterized in that
When the solvent is alkane solvents, the solvent is iso-butane;
And/or when the solvent is aromatic hydrocarbon solvent, the solvent is toluene;
And/or the alkyl imidazolium cation is 1-C1~C10Alkyl -3-C1~C10Alkylimidazolium cation;
And/or the mass ratio of the solvent and the waste sulfuric acid from alkylation is 2:1~10:1;
And/or the mass ratio of the ionic liquid and the waste sulfuric acid from alkylation is 1:1~2:1;
And/or the churned mechanically revolving speed is 100~2000r/min;
And/or the mixed temperature is 10~30 DEG C;
And/or the mixed time is 0.5~3 hour;
And/or the temperature of the liquid separation is 10~30 DEG C.
5. the processing method of waste sulfuric acid from alkylation as claimed in claim 4, which is characterized in that
The alkyl imidazolium cation is 1-C4~C8Alkyl -3-C1~C4Alkylimidazolium cation;
And/or the churned mechanically revolving speed is 500~1500r/min.
6. the processing method of waste sulfuric acid from alkylation as claimed in claim 5, which is characterized in that
The alkyl imidazolium cation is that 1- butyl -3- methyl imidazolium cation, 1- hexyl -3- methyl imidazolium cation and 1- are pungent
One of base -3- methyl imidazolium cation is a variety of.
7. the processing method of waste sulfuric acid from alkylation as described in claim 1, which is characterized in that the ionic liquid is 1- fourth
Base -3- methylimidazole hexafluorophosphate, 1- hexyl -3- methylimidazole hexafluorophosphate, 1- octyl -3- methylimidazole hexafluorophosphoric acid
Salt, 1- butyl -3- methyl imidazolium tetrafluoroborate, 1- hexyl -3- methyl imidazolium tetrafluoroborate, 1- octyl -3- methylimidazole
The double trifluoro methylsulfonyls of tetrafluoroborate, 1- butyl -3- methylimidazole bis-trifluoromethylsulfoandimide salt, 1- hexyl -3- methylimidazole
One of inferior amine salt and 1- octyl -3- methylimidazole bis-trifluoromethylsulfoandimide salt are a variety of.
8. the processing method of waste sulfuric acid from alkylation as claimed in claim 7, which is characterized in that the ionic liquid is 1- fourth
Base -3- methylimidazole bis-trifluoromethylsulfoandimide salt, 1- butyl -3- methylimidazole hexafluorophosphate, 1- butyl -3- methylimidazole
One of hexafluorophosphate and 1- hexyl -3- methyl imidazolium tetrafluoroborate are a variety of.
9. the processing method of waste sulfuric acid from alkylation as described in any one of claims 1 to 8, which is characterized in that after liquid separation also into
One step includes the recycling of the ionic liquid.
10. the processing method of waste sulfuric acid from alkylation as claimed in claim 9, which is characterized in that the mode of the recycling is
The supernatant liquid obtained after liquid separation is evaporated under reduced pressure.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910440175.7A CN110092358A (en) | 2019-05-24 | 2019-05-24 | A kind of processing method of waste sulfuric acid from alkylation |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201910440175.7A CN110092358A (en) | 2019-05-24 | 2019-05-24 | A kind of processing method of waste sulfuric acid from alkylation |
Publications (1)
Publication Number | Publication Date |
---|---|
CN110092358A true CN110092358A (en) | 2019-08-06 |
Family
ID=67449116
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201910440175.7A Pending CN110092358A (en) | 2019-05-24 | 2019-05-24 | A kind of processing method of waste sulfuric acid from alkylation |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN110092358A (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111302359A (en) * | 2020-03-13 | 2020-06-19 | 云南云天化石化有限公司 | Method for preparing ammonium sulfate from alkylation waste acid by one-step impurity removal |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE788621A (en) * | 1972-09-08 | 1973-03-08 | Texaco Development Corp | Removing hydrocarbons from spent sulphuric acid catalyst - which has been used for alkylation of olefins or aromatics |
DE2247115A1 (en) * | 1972-09-26 | 1974-03-28 | Texaco Development Corp | Removing hydrocarbons from spent sulphuric acid catalyst - which has been used for alkylation of olefins or aromatics |
CN1072905A (en) * | 1991-12-02 | 1993-06-09 | 赫彻斯特股份公司 | The method of separation of organic phosphorous compound and other impurity from dilute sulphuric acid |
CN104760938A (en) * | 2015-03-18 | 2015-07-08 | 安庆师范学院 | Method for removing iron ions from concentrated sulfuric acid |
CN107754850A (en) * | 2016-08-17 | 2018-03-06 | 中国科学院过程工程研究所 | A kind of method for preparing charcoal base acid material using the alkylation spent acid containing ionic liquid |
CN109395776A (en) * | 2017-08-17 | 2019-03-01 | 华东理工大学 | A kind of alkylated reaction catalyst system and its preparation method and application |
-
2019
- 2019-05-24 CN CN201910440175.7A patent/CN110092358A/en active Pending
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
BE788621A (en) * | 1972-09-08 | 1973-03-08 | Texaco Development Corp | Removing hydrocarbons from spent sulphuric acid catalyst - which has been used for alkylation of olefins or aromatics |
DE2247115A1 (en) * | 1972-09-26 | 1974-03-28 | Texaco Development Corp | Removing hydrocarbons from spent sulphuric acid catalyst - which has been used for alkylation of olefins or aromatics |
CN1072905A (en) * | 1991-12-02 | 1993-06-09 | 赫彻斯特股份公司 | The method of separation of organic phosphorous compound and other impurity from dilute sulphuric acid |
CN104760938A (en) * | 2015-03-18 | 2015-07-08 | 安庆师范学院 | Method for removing iron ions from concentrated sulfuric acid |
CN107754850A (en) * | 2016-08-17 | 2018-03-06 | 中国科学院过程工程研究所 | A kind of method for preparing charcoal base acid material using the alkylation spent acid containing ionic liquid |
CN109395776A (en) * | 2017-08-17 | 2019-03-01 | 华东理工大学 | A kind of alkylated reaction catalyst system and its preparation method and application |
Non-Patent Citations (2)
Title |
---|
王焕英: "疏水性离子液体萃取再生烷基化废酸", 中国优秀硕士学位论文全文数据库, no. 08, pages 41 - 50 * |
马承恕: "染料工业三废治理技术", vol. 1988, 中国化工学会染料学会染料行业环保科技情报网, pages: 179 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN111302359A (en) * | 2020-03-13 | 2020-06-19 | 云南云天化石化有限公司 | Method for preparing ammonium sulfate from alkylation waste acid by one-step impurity removal |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
Yao et al. | Efficient separation of phenol from model oils using environmentally benign quaternary ammonium-based zwitterions via forming deep eutectic solvents | |
Qin et al. | Bifunctional imidazole‐PTSA deep eutectic solvent for synthesizing long‐chain ester IBIBE in reactive extraction | |
CN102676212A (en) | Raw oil optimization method and equipment for improving aromatic hydrocarbon content of environment-friendly rubber filling oil | |
CN110092358A (en) | A kind of processing method of waste sulfuric acid from alkylation | |
CN107032308A (en) | A kind of waste sulfuric acid from alkylation resource recycle method | |
CN110015949B (en) | Method for extracting phenolic substances from raw oil containing phenol | |
CN102442951B (en) | Preparation method of functionalized polyacid-type sulfonic ionic liquid | |
CN103571524B (en) | Remove cracking c_5 total sulfur apparatus and method | |
CN102408915A (en) | Method for oil product desulfurization through oxidation and extraction | |
CN102676214B (en) | Solvent refining method and equipment for producing environment-friendly rubber filling oil | |
CN103450056A (en) | Mahogany petroleum sulfonate preparation method for oil exploitation | |
CN106866382A (en) | The extracting method of aldehydes matter in a kind of catalytic lignin depolymerization product liquid | |
CN104845662A (en) | A method for extracting phenolic compounds in coal liquefaction oil | |
CN100497537C (en) | Removal of naphthenic acid in oil using composite deacidifying agent | |
CN101665716B (en) | Composite deacidification agent and method for recovering naphthenic acid from oil | |
CN111848359B (en) | Method for separating phenolic substances in medium and low temperature coal tar | |
CN103602346A (en) | Method for desulfurizing oil through oxidation-extraction coupling | |
CN106744723A (en) | A kind of renovation process of waste sulfuric acid from alkylation | |
CN102618322A (en) | Method for desulfurizing fuel oil extracted by catalytic oxidation of carboxyl functionalized benzimidazole ionic liquid | |
CN110204475A (en) | A kind of method that double site pyrrolidone-base ionic liquid separates indoles in coal tar | |
CN106632515A (en) | Method for degrading lignin by ionic liquid catalyzed alcohol system | |
CN106010636B (en) | A kind of method that mixed acid system containing ionic liquid and nitric acid catalyzes and synthesizes alkylate oil | |
CN106675619B (en) | The method that quaternization reaction removes nitride in shale oil diesel oil distillate | |
CN104788371A (en) | Method for extracting 2-methylquinoline from isoquinoline stillage residual liquor | |
CN101255106B (en) | Method for intensified neutral oil removal of diesel alkaline residue and stepwise reclamation of naphthenic acids and phenols |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PB01 | Publication | ||
PB01 | Publication | ||
SE01 | Entry into force of request for substantive examination | ||
SE01 | Entry into force of request for substantive examination | ||
WD01 | Invention patent application deemed withdrawn after publication | ||
WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190806 |