CN105480998A - Method for preparing aluminum sulfate by catalyzing alkylated waste sulfuric acid with lignocellulose ester - Google Patents
Method for preparing aluminum sulfate by catalyzing alkylated waste sulfuric acid with lignocellulose ester Download PDFInfo
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- CN105480998A CN105480998A CN201510946136.6A CN201510946136A CN105480998A CN 105480998 A CN105480998 A CN 105480998A CN 201510946136 A CN201510946136 A CN 201510946136A CN 105480998 A CN105480998 A CN 105480998A
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- Prior art keywords
- sulfuric acid
- waste sulfuric
- lignocellulose ester
- lignocellulose
- acid
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 150000002148 esters Chemical class 0.000 title claims abstract description 94
- 239000002699 waste material Substances 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title claims abstract description 52
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 title claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 47
- 239000007788 liquid Substances 0.000 claims abstract description 41
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 14
- 239000002994 raw material Substances 0.000 claims abstract description 14
- 239000000126 substance Substances 0.000 claims abstract description 14
- 238000006479 redox reaction Methods 0.000 claims abstract description 12
- 238000000926 separation method Methods 0.000 claims abstract description 11
- 239000003337 fertilizer Substances 0.000 claims abstract description 9
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 8
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 239000002253 acid Substances 0.000 claims abstract description 6
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 60
- 238000006243 chemical reaction Methods 0.000 claims description 43
- 239000002910 solid waste Substances 0.000 claims description 37
- 230000029936 alkylation Effects 0.000 claims description 29
- 238000005804 alkylation reaction Methods 0.000 claims description 29
- 239000000843 powder Substances 0.000 claims description 26
- 238000002360 preparation method Methods 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 18
- 238000005886 esterification reaction Methods 0.000 claims description 16
- 230000008569 process Effects 0.000 claims description 16
- 230000032050 esterification Effects 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 238000000498 ball milling Methods 0.000 claims description 11
- 239000007790 solid phase Substances 0.000 claims description 11
- 238000003746 solid phase reaction Methods 0.000 claims description 11
- 239000012752 auxiliary agent Substances 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 8
- 238000010298 pulverizing process Methods 0.000 claims description 8
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- POULHZVOKOAJMA-UHFFFAOYSA-N dodecanoic acid Chemical compound CCCCCCCCCCCC(O)=O POULHZVOKOAJMA-UHFFFAOYSA-N 0.000 claims description 6
- WWZKQHOCKIZLMA-UHFFFAOYSA-N octanoic acid Chemical compound CCCCCCCC(O)=O WWZKQHOCKIZLMA-UHFFFAOYSA-N 0.000 claims description 6
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 150000001735 carboxylic acids Chemical group 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000005639 Lauric acid Substances 0.000 claims description 3
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001413 amino acids Chemical class 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- 239000003570 air Substances 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 150000003384 small molecules Chemical class 0.000 claims description 2
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims 2
- 159000000013 aluminium salts Chemical class 0.000 claims 2
- 229910000329 aluminium sulfate Inorganic materials 0.000 claims 2
- 238000004137 mechanical activation Methods 0.000 claims 2
- 239000002361 compost Substances 0.000 claims 1
- 238000005469 granulation Methods 0.000 claims 1
- 230000003179 granulation Effects 0.000 claims 1
- 238000000227 grinding Methods 0.000 claims 1
- 238000010671 solid-state reaction Methods 0.000 claims 1
- 239000007800 oxidant agent Substances 0.000 abstract description 23
- 238000002386 leaching Methods 0.000 abstract description 18
- 239000005416 organic matter Substances 0.000 abstract description 15
- 230000001590 oxidative effect Effects 0.000 abstract description 11
- 238000004519 manufacturing process Methods 0.000 abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 9
- 238000004042 decolorization Methods 0.000 abstract description 5
- 239000012452 mother liquor Substances 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 abstract description 3
- 230000003213 activating effect Effects 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 239000012535 impurity Substances 0.000 abstract description 2
- 239000012295 chemical reaction liquid Substances 0.000 abstract 2
- 239000000047 product Substances 0.000 description 26
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 12
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 12
- 230000004913 activation Effects 0.000 description 10
- 238000001035 drying Methods 0.000 description 9
- 239000003895 organic fertilizer Substances 0.000 description 9
- 239000012374 esterification agent Substances 0.000 description 8
- 240000003183 Manihot esculenta Species 0.000 description 6
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 6
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 6
- 235000019341 magnesium sulphate Nutrition 0.000 description 6
- BNVZOJUDDYZFQY-UHFFFAOYSA-N [S].[Mg].[Ca].[Si] Chemical compound [S].[Mg].[Ca].[Si] BNVZOJUDDYZFQY-UHFFFAOYSA-N 0.000 description 5
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 241000609240 Ambelania acida Species 0.000 description 3
- 240000000249 Morus alba Species 0.000 description 3
- 235000008708 Morus alba Nutrition 0.000 description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 3
- 239000010905 bagasse Substances 0.000 description 3
- 238000010525 oxidative degradation reaction Methods 0.000 description 3
- 239000010902 straw Substances 0.000 description 3
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 244000082204 Phyllostachys viridis Species 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 239000011575 calcium Substances 0.000 description 2
- 229910052791 calcium Inorganic materials 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000003502 gasoline Substances 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000002023 wood Substances 0.000 description 2
- 235000016623 Fragaria vesca Nutrition 0.000 description 1
- 240000009088 Fragaria x ananassa Species 0.000 description 1
- 235000011363 Fragaria x ananassa Nutrition 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- NHTMVDHEPJAVLT-UHFFFAOYSA-N Isooctane Chemical compound CC(C)CC(C)(C)C NHTMVDHEPJAVLT-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- 206010035148 Plague Diseases 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241000607479 Yersinia pestis Species 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 239000006229 carbon black Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 235000010675 chips/crisps Nutrition 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- JVSWJIKNEAIKJW-UHFFFAOYSA-N dimethyl-hexane Natural products CCCCCC(C)C JVSWJIKNEAIKJW-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000001095 magnesium carbonate Substances 0.000 description 1
- ZLNQQNXFFQJAID-UHFFFAOYSA-L magnesium carbonate Chemical compound [Mg+2].[O-]C([O-])=O ZLNQQNXFFQJAID-UHFFFAOYSA-L 0.000 description 1
- 235000014380 magnesium carbonate Nutrition 0.000 description 1
- 229910000021 magnesium carbonate Inorganic materials 0.000 description 1
- WRUGWIBCXHJTDG-UHFFFAOYSA-L magnesium sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Mg+2].[O-]S([O-])(=O)=O WRUGWIBCXHJTDG-UHFFFAOYSA-L 0.000 description 1
- 229940061634 magnesium sulfate heptahydrate Drugs 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000000638 stimulation Effects 0.000 description 1
- 239000001384 succinic acid Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 238000009279 wet oxidation reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/68—Aluminium compounds containing sulfur
- C01F7/74—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Fertilizers (AREA)
- Catalysts (AREA)
Abstract
一种木质纤维素酯催化处理烷基化废硫酸制备硫酸铝的方法，将烷基化废硫酸加入到氧化铝或氢氧化铝中反应，至其pH值为弱酸性，得到混合液，将混合液过滤得到浸出渣和反应液；然后在反应液中加入催化剂木质纤维素酯和氧化剂发生氧化还原反应，将烷基化废硫酸中的有机物完全转化为CO2、H2O、N2等无害小分子物质，固液分离，得到纤维质滤渣和精制液，最后将精制液结晶后即可得工业级硫酸铝产品。本发明所选用的木质纤维素酯不仅具有催化功能，而且还具有活化氧化剂及吸附脱色功能；生产过程没有引入其它杂质，不会造成二次污染，废酸中的有机物得到氧化降解，母液全部循环利用，不会影响产品质量，产品质量达到工业级的质量标准；生产工艺操作简单、常压操作，安全可靠，投资省；木质纤维素酯催化剂可生物降解，可作为生物肥料的原料，生产过程无三废排放。A method for preparing aluminum sulfate by catalytically treating alkylated waste sulfuric acid with lignocellulose esters. The alkylated waste sulfuric acid is added to aluminum oxide or aluminum hydroxide to react until the pH value is weakly acidic to obtain a mixed solution, which is mixed with Liquid filtration to obtain leaching residue and reaction liquid; then add catalyst lignocellulose ester and oxidant to the reaction liquid to undergo redox reaction, and completely convert the organic matter in the alkylated waste sulfuric acid into CO 2 , H 2 O, N 2 and other free Harmful small molecular substances, solid-liquid separation, fibrous filter residue and refined liquid are obtained, and finally the refined liquid is crystallized to obtain industrial-grade aluminum sulfate products. The lignocellulose ester selected in the present invention not only has catalytic function, but also has the function of activating oxidant and adsorption decolorization; no other impurities are introduced in the production process, which will not cause secondary pollution, the organic matter in the waste acid is oxidatively degraded, and the mother liquor is completely recycled Utilization will not affect the product quality, and the product quality reaches the industrial quality standard; the production process is simple to operate, normal pressure operation, safe and reliable, and low investment; the lignocellulose ester catalyst is biodegradable and can be used as a raw material for biological fertilizers. No waste discharge.
Description
技术领域technical field
本发明属于有机废水处理领域，具体地说是一种木质纤维素酯作为氧化催化剂应用于处理烷基化废硫酸并制备硫酸铝的方法。The invention belongs to the field of organic wastewater treatment, in particular to a method in which lignocellulose ester is used as an oxidation catalyst to treat alkylation waste sulfuric acid and prepare aluminum sulfate.
背景技术Background technique
随着国际对燃油要求的提高，目前炼油厂广泛采用烷基化法生产异辛烷，产量飞速增加。以烷基化装置加工生产高辛烷值的烷基化汽油时，需用浓度为98％的硫酸作为催化剂，每生产1吨烷基化汽油就产生80～100kg废硫酸，废硫酸中含90％左右的硫酸，7％左右的有机物和3％左右的水。有机物主要是高分子烯烃、二烯烃、烷基磺酸、硫酸酯以及硫化物等，这些物质颜色深、质地粘稠、气味刺激，很难从硫酸中彻底除去。现有的成熟处理技术主要是裂解再生成硫酸回用，但设备投资巨大，而且处理每吨废硫酸的费用高、亏损巨大，这对生产企业的成本和环境带来了极大的压力，是困扰企业生产的最大难题。其他有萃取等处理工艺，但萃取溶剂回收成本高、硫酸含量低，尚未见到有应用的企业。此外，利用烷基化废硫酸生产硫酸铵、硫酸镁、活性白土、沉淀白炭黑、石油防锈剂等也有研究，但由于不能有效降解脱除废硫酸中的有机物，产品有较强的刺激性气味，难以得到高纯度的产品，而且加入的处理剂容易造成二次污染，母液难以循环利用。因此，目前烷基化废硫酸仍然得不到有效处理，在生产企业大量积压，使企业面临停产的风险，这将给企业带来巨大的经济损失。With the improvement of international requirements for fuel oil, the alkylation method is widely used in refineries to produce isooctane, and the output is increasing rapidly. When using an alkylation unit to process and produce high-octane alkylated gasoline, sulfuric acid with a concentration of 98% must be used as a catalyst. Every ton of alkylated gasoline produced will produce 80-100kg of waste sulfuric acid, which contains 90 % of sulfuric acid, about 7% of organic matter and about 3% of water. The organic substances are mainly polymer olefins, diolefins, alkylsulfonic acids, sulfuric acid esters, and sulfides. These substances have dark color, sticky texture, and irritating odor, and it is difficult to completely remove them from sulfuric acid. The existing mature treatment technology is mainly to crack and regenerate sulfuric acid for reuse, but the equipment investment is huge, and the cost of processing each ton of waste sulfuric acid is high and the loss is huge, which brings great pressure on the cost of the production enterprise and the environment. The biggest problem that plagues the production of enterprises. There are other treatment processes such as extraction, but the recovery cost of extraction solvent is high and the content of sulfuric acid is low, so there are no enterprises that have applied it. In addition, the use of alkylated waste sulfuric acid to produce ammonium sulfate, magnesium sulfate, activated clay, precipitated white carbon black, petroleum rust inhibitors, etc. has also been studied, but because the organic matter in the waste sulfuric acid cannot be effectively degraded and removed, the product has a strong stimulation Strong odor, it is difficult to obtain high-purity products, and the added treatment agent is likely to cause secondary pollution, and the mother liquor is difficult to recycle. Therefore, at present, the alkylation waste sulfuric acid still cannot be effectively treated, and there is a large backlog in the production enterprises, which makes the enterprises face the risk of stopping production, which will bring huge economic losses to the enterprises.
中国专利名称:一种利用烷基化废硫酸生产硫酸镁和硅钙硫镁肥的方法；申请(专利)号:CN201410207898.X；申请日:2014.05.18；公开(公告)号:CN104016385A；公开(公告)日:2014.09.03；该发明公开了一种利用烷基化废硫酸生产硫酸镁和硅钙硫镁肥的方法，通过生产硫酸镁消耗硫酸，利用矿粉中硅、钙等悬浮物吸附分离出酸性油废渣，利用含油渣的热量和废活性炭的热量辅助外加热源煅烧废渣，使有机物碳化，生产主要含有硅钙镁硫的肥料。本发明的有益效果是：该方法工艺简单、操作简便、易于实施，而且设备投资少、成本低、无二次污染、副产品硅钙硫镁肥市场需求大、经济和社会效益显著，本发明使所有资源都得到了最优化使用，是处理烷基化废酸的低成本、理想工艺。主权项:一种利用烷基化废硫酸生产硫酸镁和硅钙硫镁肥的方法，其特征在于步骤如下：1)将烷基化废硫酸预热到60-100℃，加入到有搅拌的菱镁矿粉悬浮液中并反应到基本无气泡，再加入轻烧粉进行反应至ph为6.5-7.2，得到混合液；2)将上述混合液压滤分离得到一次母液和一次废渣，在一次母液中加入氧化剂和活性碳并搅拌脱色后，再次压滤得到精制母液和活性炭废渣，精制母液经过结晶、离心、烘干，制得七水硫酸镁；3)将一次废渣和活性炭废渣混合均匀，在700-1100℃下进行煅烧后，用硫酸镁粉末造粒，即可制得硅钙硫镁肥。但是该方法选用的氧化剂比较昂贵，工艺成本较高；该方法选用活性炭进行脱色，活性炭容易吸附饱和，脱色往往不彻底。Chinese patent name: A method for producing magnesium sulfate and silicon calcium sulfur magnesium fertilizer by using alkylated waste sulfuric acid; application (patent) number: CN201410207898.X; application date: 2014.05.18; publication (announcement) number: CN104016385A; publication (Announcement) Date: 2014.09.03; the invention discloses a method for producing magnesium sulfate and silicon-calcium-sulfur-magnesium fertilizer by using alkylated waste sulfuric acid, consuming sulfuric acid through the production of magnesium sulfate, and utilizing suspended matter such as silicon and calcium in mineral powder The acidic oil waste residue is separated by adsorption, and the heat of the oily residue and the heat of the waste activated carbon are used to assist the external heating source to calcine the waste residue, carbonize the organic matter, and produce fertilizers mainly containing silicon, calcium, magnesium, and sulfur. The beneficial effects of the present invention are: the method is simple in process, easy to operate, easy to implement, and has less equipment investment, low cost, no secondary pollution, large market demand for by-product silicon calcium sulfur magnesium fertilizer, and remarkable economic and social benefits. All resources are used optimally and it is a low-cost, ideal process for treating spent acid from alkylation. Sovereignty item: A method for producing magnesium sulfate and silicon-calcium-sulfur-magnesium fertilizer by using alkylated waste sulfuric acid, characterized in that the steps are as follows: 1) preheating the alkylated waste sulfuric acid to 60-100°C, adding it to a stirring into the suspension of magnesite powder and react until there are no bubbles, and then add lightly burned powder to react until the pH is 6.5-7.2 to obtain a mixed solution; 2) separate the above-mentioned mixed hydraulic pressure to obtain a primary mother liquor and a primary waste residue. After adding oxidizing agent and activated carbon and stirring and decolorizing, press filter again to obtain refined mother liquor and activated carbon waste residue, and the refined mother liquor is through crystallization, centrifugation and drying to obtain magnesium sulfate heptahydrate; 3) mix the primary waste residue and activated carbon waste residue evenly, and After calcining at 700-1100°C, granulate with magnesium sulfate powder to obtain silicon calcium sulfur magnesium fertilizer. However, the oxidizing agent selected by this method is relatively expensive, and the process cost is relatively high; this method selects activated carbon for decolorization, and activated carbon is easy to absorb and saturate, and the decolorization is often incomplete.
发明内容Contents of the invention
针对上述存在的问题，本发明开发了一种木质纤维素酯催化处理烷基化废硫酸制备硫酸铝的方法，该方法处理后的废渣、精制液均无刺激性气味，精制液清澈透明，精制液经结晶后得到高纯度的硫酸铝，作为废弃物的浸出渣和纤维质滤渣混合后进行有机堆肥得到可降解的有机肥基料。In view of the above-mentioned problems, the present invention has developed a method for preparing aluminum sulfate by catalytically treating alkylated waste sulfuric acid with lignocellulose ester. The waste residue and refined liquid after the treatment by the method have no irritating smell, and the refined liquid is clear and transparent. The liquid is crystallized to obtain high-purity aluminum sulfate, and the leaching residue used as waste and fibrous filter residue are mixed and then organically composted to obtain a degradable organic fertilizer base material.
本发明的具体技术方案如下：Concrete technical scheme of the present invention is as follows:
一种木质纤维素酯催化处理烷基化废硫酸制备硫酸铝的方法，将烷基化废硫酸加入到氧化铝或氢氧化铝中反应，至其pH值为弱酸性，得到混合液，将混合液过滤得到浸出渣和反应液；然后在反应液中加入催化剂木质纤维素酯和氧化剂发生氧化还原反应，将烷基化废硫酸中的有机物通过深度氧化降解转化为CO2、H2O、N2等无害小分子物质，固液分离，得到纤维质滤渣和精制液，最后将精制液结晶后即可得到工业级硫酸铝产品。A method for preparing aluminum sulfate by catalytically treating alkylated waste sulfuric acid with lignocellulose esters. The alkylated waste sulfuric acid is added to aluminum oxide or aluminum hydroxide to react until the pH value is weakly acidic to obtain a mixed solution, which is mixed with Liquid filtration to obtain leaching residue and reaction solution; then add catalyst lignocellulose ester and oxidant to the reaction solution to undergo redox reaction, and convert the organic matter in the alkylated waste sulfuric acid into CO 2 , H 2 O, N through deep oxidation degradation 2 and other harmless small molecular substances, solid-liquid separation to obtain fibrous filter residue and refined liquid, and finally the refined liquid is crystallized to obtain industrial-grade aluminum sulfate products.
以上所述的木质纤维素酯催化处理烷基化废硫酸制备硫酸铝的方法，所述的木质纤维素酯制备方法包括以下步骤：The method for preparing aluminum sulfate by catalytically treating alkylation waste sulfuric acid with lignocellulose ester described above, the preparation method of described lignocellulose ester comprises the following steps:
(1)原料预处理：将纤维质固废物干燥、粉碎得到纤维质固废物粉末；(1) raw material pretreatment: drying and pulverizing the fibrous solid waste to obtain fibrous solid waste powder;
(2)高速混合：按纤维质固废物粉末、酯化剂及助剂100：5-40：1-8的比例加入到混合机混合均匀，得到混合物；(2) High-speed mixing: add the fibrous solid waste powder, esterification agent and auxiliary agent in the ratio of 100:5-40:1-8 to the mixer and mix evenly to obtain a mixture;
(3)机械活化固相反应：将上述混合物磨介质堆体积按照100g:200-600ml的比例加入机械活化固相反应器中，在转速为200-600rpm和30-60℃恒温水浴温度下进行球磨反应，达到0.5-1.5h活化时间后，停止搅拌，取出酯化产物和磨球，并将它们分离，得到木质纤维素酯混合物；(3) Mechanically activated solid-phase reaction: add the above-mentioned mixture into the mechanically activated solid-phase reactor according to the ratio of 100g:200-600ml of the volume of the milling medium, and perform ball milling at a speed of 200-600rpm and a temperature of 30-60°C in a constant temperature water bath After the reaction reaches the activation time of 0.5-1.5h, stop the stirring, take out the esterification product and the balls, and separate them to obtain the lignocellulose ester mixture;
(4)后处理：木质纤维素酯混合物进行造粒成球即可得到木质纤维素酯催化剂。(4) Post-treatment: the lignocellulose ester mixture is granulated into balls to obtain the lignocellulose ester catalyst.
以上所述的木质纤维素酯催化处理烷基化废硫酸制备硫酸铝的方法，所述的酯化剂为羧基酸，所述的羧基酸包括琥珀酸、马来酸、草酸、柠檬酸、丁酸、乙醇酸、氨基酸、正辛酸，月桂酸任一一种或两种以上的组合。The method for preparing aluminum sulfate by catalytically treating alkylation waste sulfuric acid with lignocellulose ester described above, the esterification agent is a carboxylic acid, and the carboxylic acid includes succinic acid, maleic acid, oxalic acid, citric acid, butyric acid Acid, glycolic acid, amino acid, n-caprylic acid, lauric acid, any one or a combination of two or more.
以上任一所述的木质纤维素酯催化处理烷基化废硫酸制备硫酸铝的方法，所述的助剂为酯化反应催化剂，所述的酯化反应催化剂为铝盐，所述的铝盐为AlCl3、Al(NO3)3、Al2(SO4)3中的一种或者两种的混合物。The method for preparing aluminum sulfate by catalytically treating alkylation waste sulfuric acid with any one of the above lignocellulose esters, the auxiliary agent is an esterification catalyst, and the esterification catalyst is an aluminum salt, and the aluminum salt It is one or a mixture of AlCl 3 , Al(NO 3 ) 3 , Al 2 (SO4) 3 .
根据本领域普通技术人员的常熟，所述的纤维质固废物为甘蔗渣、木薯酒糟、木薯杆、木屑、竹屑、秸秆、桑枝任一一种或两种以上的组合。所述的干燥为将纤维质固废物干燥到含水量小于15％，所述的粉碎为将纤维质固废物粉碎到过20-60目筛。According to those skilled in the art, the fibrous solid waste is any one or a combination of two or more of bagasse, cassava distiller's grains, cassava stalks, wood chips, bamboo chips, straw, and mulberry branches. The drying is to dry the fibrous solid waste until the water content is less than 15%, and the crushing is to crush the fibrous solid waste to pass through a 20-60 mesh sieve.
以上所述的木质纤维素酯催化处理烷基化废硫酸制备硫酸铝的方法，所述的氧化剂为空气、氧气、双氧水和臭氧中的一种。In the method for preparing aluminum sulfate by catalytically treating alkylated waste sulfuric acid with lignocellulose ester, the oxidizing agent is one of air, oxygen, hydrogen peroxide and ozone.
以上所述的木质纤维素酯催化处理烷基化废硫酸制备硫酸铝的方法，所述的催化剂和氧化剂加入的质量分别为废硫酸质量的0.2-5％和1-20％，氧化铝或氢氧化铝加入的质量为废硫酸质量的25-50％。The above-mentioned method for preparing aluminum sulfate by catalytically treating alkylation waste sulfuric acid with lignocellulose esters, the quality of the catalyst and oxidant added are respectively 0.2-5% and 1-20% of the waste sulfuric acid mass, aluminum oxide or hydrogen The quality of alumina added is 25-50% of the quality of waste sulfuric acid.
以上所述的木质纤维素酯催化处理烷基化废硫酸制备硫酸铝的方法，所述氧化还原反应条件为反应温度在30-80℃，反应时间30-180min。The above-mentioned method for preparing aluminum sulfate by catalytically treating alkylated waste sulfuric acid with lignocellulose esters, the redox reaction conditions are that the reaction temperature is 30-80° C., and the reaction time is 30-180 minutes.
以上任一所述的木质纤维素酯催化处理烷基化废硫酸制备硫酸铝的方法，所述的弱酸性pH值为1.0-3.0。In the method for preparing aluminum sulfate by catalytically treating alkylation waste sulfuric acid with lignocellulose ester described above, the weakly acidic pH value is 1.0-3.0.
以上任一所述的木质纤维素酯催化处理烷基化废硫酸制备硫酸铝的方法，其特征在于：所述浸出渣和纤维质滤渣混合后进行有机堆肥得到可降解的有机肥基料。The method for preparing aluminum sulfate by catalytically treating alkylation waste sulfuric acid with lignocellulose ester as described above is characterized in that: the leaching residue and the fibrous filter residue are mixed and organically composted to obtain a degradable organic fertilizer base material.
本发明的技术效果和优点：Technical effect and advantage of the present invention:
(1)本发明所选用的木质纤维素酯表面含有大量酸性或碱性基团，特别是羟基、酚羟基、羧基等，具有催化、活化氧化的功能，能催化氧化剂产生强氧化性的活性自由基或原子氧，使氧化剂活化、加速反应物降解，同时，催化剂通过络合等作用加速了体系中氧原子的传递，同样增强了体系氧化作用。该方法处理后的纤维质滤渣和精制液均无刺激性气味，精制液清澈透明。现有的技术不能完全有效降解脱除废硫酸中的有机物，仍有较强的刺激性气味和较深的颜色。(1) The surface of the lignocellulose ester selected by the present invention contains a large number of acidic or basic groups, especially hydroxyl, phenolic hydroxyl, carboxyl, etc., which have the function of catalyzing and activating oxidation, and can catalyze the oxidizing agent to produce strong oxidizing active freedom At the same time, the catalyst accelerates the transfer of oxygen atoms in the system through complexation and other effects, and also enhances the oxidation of the system. Both the fibrous filter residue and the refined liquid treated by the method have no irritating smell, and the refined liquid is clear and transparent. Existing technologies cannot completely and effectively degrade and remove organic matter in waste sulfuric acid, and still have strong pungent odor and dark color.
(2)本发明所选用的木质纤维素酯属于催化湿式氧化法处理有机废水的非均相催化剂，在它的催化作用下，使氧化剂迅速反应分解出活性基团(自由基)，进而氧化分解有机物，最终产物为CO2、H2O及N2等无害物质，固液分离，得到纤维质滤渣和精制液，最后将精制液结晶后即可得到工业级硫酸铝产品。而现有技术制备得到的硫酸铝的纯度虽然可以达到工业级，但是外观较差，且会有刺激性气味。(2) The selected lignocellulose ester of the present invention belongs to the heterogeneous catalyst of catalytic wet oxidation process organic waste water, under its catalysis, makes oxidizing agent react rapidly and decompose active group (free radical), and then oxidizes and decomposes Organic matter, the final product is harmless substances such as CO 2 , H 2 O and N 2 , solid-liquid separation to obtain fibrous filter residue and refined liquid, and finally the refined liquid is crystallized to obtain industrial-grade aluminum sulfate products. And although the purity of the aluminum sulfate prepared by the prior art can reach industrial grade, the appearance is relatively poor, and there is a pungent smell.
(2)本发明所选用的木质纤维素酯同时还具有吸附脱色功能，能选择吸附重金属和提高脱色效果。(2) The lignocellulose ester selected in the present invention also has the function of adsorption and decolorization, which can selectively adsorb heavy metals and improve the decolorization effect.
(3)本发明所选用的木质纤维素酯不含重金属，不会出现重金属溶出所带的二次污染。(3) The lignocellulose ester selected by the present invention does not contain heavy metals, and there will be no secondary pollution caused by the dissolution of heavy metals.
(4)本发明所选用的木质纤维素酯无毒且可完全生物降解，有机废水的氧化降解产物主要为水和二氧化碳及少量无毒的小分子。(4) The lignocellulose ester selected in the present invention is nontoxic and fully biodegradable, and the oxidative degradation products of organic wastewater are mainly water, carbon dioxide and a small amount of nontoxic small molecules.
(5)本发明所选用的木质纤维素酯在制备时就选用铝盐作为酯化反应的催化剂，有效减少了其他化学杂质的引入，使得最后制备的硫酸铝的纯度得以较大提高。(5) The selected lignocellulose ester of the present invention just selects aluminum salt as the catalyzer of esterification during preparation, effectively reduces the introduction of other chemical impurities, makes the purity of the aluminum sulfate of last preparation be able to improve greatly.
(6)本发明所选用的木质纤维素酯在制备时选用的原料为固废物且制备工艺简单，成本低，添加量少，因此催化剂不考虑重复使用，经固液分离并脱附重金属离子后可作用生物肥原料。(6) The selected lignocellulose ester of the present invention is prepared by using solid waste as a raw material, and the preparation process is simple, the cost is low, and the addition amount is small, so the catalyst does not consider repeated use. After solid-liquid separation and desorption of heavy metal ions It can be used as raw material of biological fertilizer.
(7)应用本发明所选用的木质纤维素酯催化有机废水氧化降解可在常压下进行，只需要带搅拌的氧化降解反应器，操作简便。特别是应用在已有废水处理系统时不需改变原来处理工艺，可直接应用。(7) The oxidative degradation of organic waste water catalyzed by the lignocellulose ester selected in the present invention can be carried out under normal pressure, only needs a stirred oxidative degradation reactor, and is easy to operate. Especially when it is applied to the existing wastewater treatment system, it can be directly applied without changing the original treatment process.
具体实施方式detailed description
木质纤维素酯催化剂的制备Preparation of lignocellulose ester catalyst
实施例1Example 1
木质纤维素酯催化剂的制备，该制备方法包括以下步骤：The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1)原料预处理：将甘蔗渣纤维质固废物干燥至含水量小于15％、粉碎得到过20目筛的纤维质固废物粉末；(1) raw material pretreatment: drying the bagasse fibrous solid waste to a moisture content of less than 15%, pulverizing to obtain a fibrous solid waste powder passing through a 20-mesh sieve;
(2)高速混合：将纤维质固废物粉末、酯化剂琥珀酸及助剂AlCl3按100：5：1的比例加入到混合机混合均匀，得到混合物；(2) High-speed mixing: Add fibrous solid waste powder, esterification agent succinic acid and auxiliary agent AlCl3 to the mixer in a ratio of 100:5:1 and mix evenly to obtain a mixture;
(3)机械活化固相反应：将上述混合物磨介质堆体积按照100g:200ml的比例加入机械活化固相反应器中，在转速为200rpm和30℃恒温水浴温度下进行球磨反应，达到0.5h活化时间后，停止搅拌，取出酯化产物和磨球，并将它们分离，得到木质纤维素酯混合物；(3) Mechanically activated solid-phase reaction: Add the above-mentioned mixture into the mechanically activated solid-phase reactor according to the ratio of 100g:200ml of the volume of the milling medium, and perform ball milling reaction at a speed of 200rpm and a constant temperature water bath temperature of 30°C to achieve 0.5h activation After a period of time, stop stirring, take out the esterification product and the balls, and separate them to obtain a lignocellulose ester mixture;
(4)后处理：木质纤维素酯混合物进行造粒成球即可得到木质纤维素酯催化剂。(4) Post-treatment: the lignocellulose ester mixture is granulated into balls to obtain the lignocellulose ester catalyst.
实施例2Example 2
木质纤维素酯催化剂的制备，该制备方法包括以下步骤：The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1)原料预处理：将木薯酒糟纤维质固废物干燥至含水量小于10％、粉碎得到过25目筛的纤维质固废物粉末；(1) Raw material pretreatment: drying cassava distiller's grains fibrous solid waste to a moisture content of less than 10%, pulverizing to obtain fibrous solid waste powder passing through a 25-mesh sieve;
(2)高速混合：将纤维质固废物粉末、酯化剂马来酸及助剂Al(NO3)3按100：10：2的比例加入到混合机混合均匀，得到混合物；(2) High-speed mixing: Add fibrous solid waste powder, esterification agent maleic acid and auxiliary agent Al(NO 3 ) 3 into the mixer in a ratio of 100:10:2 and mix evenly to obtain a mixture;
(3)机械活化固相反应：将上述混合物磨介质堆体积按照100g:250ml的比例加入机械活化固相反应器中，在转速为250rpm和35℃恒温水浴温度下进行球磨反应，达到0.6h活化时间后，停止搅拌，取出酯化产物和磨球，并将它们分离，得到木质纤维素酯混合物；(3) Mechanically activated solid-phase reaction: add the volume of the above-mentioned mixture into the mechanically activated solid-phase reactor according to the ratio of 100g:250ml, and perform ball milling reaction at a speed of 250rpm and a constant temperature water bath temperature of 35°C to achieve 0.6h activation After a period of time, stop stirring, take out the esterification product and the balls, and separate them to obtain a lignocellulose ester mixture;
(4)后处理：木质纤维素酯混合物进行造粒成球即可得到木质纤维素酯催化剂。(4) Post-treatment: the lignocellulose ester mixture is granulated into balls to obtain the lignocellulose ester catalyst.
实施例3Example 3
木质纤维素酯催化剂的制备，该制备方法包括以下步骤：The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1)原料预处理：将木薯杆纤维质固废物干燥至含水量小于5％、粉碎得到过30目筛的纤维质固废物粉末；(1) raw material pretreatment: drying cassava stalk fibrous solid waste to a water content less than 5%, pulverizing to obtain fibrous solid waste powder passing through a 30-mesh sieve;
(2)高速混合：将纤维质固废物粉末、酯化剂草酸及助剂Al2(SO4)3按100：15：3的比例加入到混合机混合均匀，得到混合物；(2) High-speed mixing: Add fibrous solid waste powder, esterification agent oxalic acid and auxiliary agent Al 2 (SO4) 3 into the mixer in a ratio of 100:15:3 and mix evenly to obtain a mixture;
(3)机械活化固相反应：将上述混合物磨介质堆体积按照100g:300ml的比例加入机械活化固相反应器中，在转速为300rpm和40℃恒温水浴温度下进行球磨反应，达到0.7h活化时间后，停止搅拌，取出酯化产物和磨球，并将它们分离，得到木质纤维素酯混合物；(3) Mechanically activated solid-phase reaction: add the above-mentioned mixture into the mechanically activated solid-phase reactor according to the ratio of 100g:300ml, and perform ball milling reaction at a speed of 300rpm and a temperature of 40°C constant temperature water bath to achieve 0.7h activation After a period of time, stop stirring, take out the esterification product and the balls, and separate them to obtain a lignocellulose ester mixture;
(4)后处理：木质纤维素酯混合物进行造粒成球即可得到木质纤维素酯催化剂。(4) Post-treatment: the lignocellulose ester mixture is granulated into balls to obtain the lignocellulose ester catalyst.
实施例4Example 4
木质纤维素酯催化剂的制备，该制备方法包括以下步骤：The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1)原料预处理：将木屑纤维质固废物干燥至含水量小于15％、粉碎得到过35目筛的纤维质固废物粉末；(1) Raw material pretreatment: drying the wood chip fibrous solid waste until the water content is less than 15%, pulverizing to obtain the fibrous solid waste powder passing through a 35-mesh sieve;
(2)高速混合：将纤维质固废物粉末、酯化剂柠檬酸及助剂(AlCl3、Al(NO3)3按任意比例混合的混合物)按100：20：4的比例加入到混合机混合均匀，得到混合物；(2) High-speed mixing: Add fibrous solid waste powder, esterifying agent citric acid and additives (a mixture of AlCl 3 , Al(NO 3 ) 3 in any proportion) to the mixer at a ratio of 100:20:4 Mix well to get a mixture;
(3)机械活化固相反应：将上述混合物磨介质堆体积按照100g:350ml的比例加入机械活化固相反应器中，在转速为350rpm和45℃恒温水浴温度下进行球磨反应，达到0.8h活化时间后，停止搅拌，取出酯化产物和磨球，并将它们分离，得到木质纤维素酯混合物；(3) Mechanically activated solid-phase reaction: add the volume of the above mixture to the mechanically activated solid-phase reactor according to the ratio of 100g:350ml, and perform ball milling reaction at a speed of 350rpm and a constant temperature water bath temperature of 45°C to achieve 0.8h activation After a period of time, stop stirring, take out the esterification product and the balls, and separate them to obtain a lignocellulose ester mixture;
(4)后处理：木质纤维素酯混合物进行造粒成球即可得到木质纤维素酯催化剂。(4) Post-treatment: the lignocellulose ester mixture is granulated into balls to obtain the lignocellulose ester catalyst.
实施例5Example 5
木质纤维素酯催化剂的制备，该制备方法包括以下步骤：The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1)原料预处理：将竹屑纤维质固废物干燥至含水量小于5％、粉碎得到过40目筛的纤维质固废物粉末；(1) raw material pretreatment: drying the bamboo chips fibrous solid waste to a moisture content of less than 5%, pulverizing to obtain the fibrous solid waste powder passing through a 40-mesh sieve;
(2)高速混合：将纤维质固废物粉末、酯化剂丁酸及助剂(AlCl3、、Al2(SO4)3按任意比例混合的混合物)按100：25：5的比例加入到混合机混合均匀，得到混合物；(2) High-speed mixing: Add fibrous solid waste powder, esterification agent butyric acid and additives (AlCl 3 , Al 2 (SO4) 3 mixed in any proportion) to the mixing chamber at a ratio of 100:25:5 machine to mix evenly to obtain a mixture;
(3)机械活化固相反应：将上述混合物磨介质堆体积按照100g:400ml的比例加入机械活化固相反应器中，在转速为400rpm和50℃恒温水浴温度下进行球磨反应，达到0.9h活化时间后，停止搅拌，取出酯化产物和磨球，并将它们分离，得到木质纤维素酯混合物；(3) Mechanically activated solid-phase reaction: add the above-mentioned mixture into the mechanically activated solid-phase reactor according to the ratio of 100g:400ml of the mass of the milling medium, and perform ball milling reaction at a speed of 400rpm and a temperature of 50°C constant temperature water bath to achieve 0.9h activation After a period of time, stop stirring, take out the esterification product and the balls, and separate them to obtain a lignocellulose ester mixture;
(4)后处理：木质纤维素酯混合物进行造粒成球即可得到木质纤维素酯催化剂。(4) Post-treatment: the lignocellulose ester mixture is granulated into balls to obtain the lignocellulose ester catalyst.
实施例6Example 6
木质纤维素酯催化剂的制备，该制备方法包括以下步骤：The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1)原料预处理：将秸秆纤维质固废物干燥至含水量小于8％、粉碎得到过45目筛的纤维质固废物粉末；(1) Raw material pretreatment: drying the straw fibrous solid waste until the water content is less than 8%, and pulverizing to obtain the fibrous solid waste powder passing through a 45-mesh sieve;
(2)高速混合：将纤维质固废物粉末、酯化剂氨基酸及助剂(Al(NO3)3、Al2(SO4)3按任意比例混合的混合物)按100：30：6的比例加入到混合机混合均匀，得到混合物；(2) High-speed mixing: Add fibrous solid waste powder, esterifying agent, amino acid and additives (a mixture of Al(NO 3 ) 3 , Al 2 (SO4) 3 in any proportion) in a ratio of 100:30:6 Go to the mixer and mix evenly to get the mixture;
(3)机械活化固相反应：将上述混合物磨介质堆体积按照100g:450ml的比例加入机械活化固相反应器中，在转速为450rpm和55℃恒温水浴温度下进行球磨反应，达到1.0h活化时间后，停止搅拌，取出酯化产物和磨球，并将它们分离，得到木质纤维素酯混合物；(3) Mechanically activated solid-phase reaction: add the volume of the above-mentioned mixture into the mechanically activated solid-phase reactor according to the ratio of 100g:450ml, and perform ball milling reaction at a speed of 450rpm and a constant temperature water bath temperature of 55°C to achieve 1.0h activation After a period of time, stop stirring, take out the esterification product and the balls, and separate them to obtain a lignocellulose ester mixture;
(4)后处理：木质纤维素酯混合物进行造粒成球即可得到木质纤维素酯催化剂。(4) Post-treatment: the lignocellulose ester mixture is granulated into balls to obtain the lignocellulose ester catalyst.
实施例7Example 7
木质纤维素酯催化剂的制备，该制备方法包括以下步骤：The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1)原料预处理：将桑枝纤维质固废物干燥至含水量小于15％、粉碎得到过50目筛的纤维质固废物粉末；(1) raw material pretreatment: dry the mulberry branch fibrous solid waste to a moisture content of less than 15%, pulverize to obtain the fibrous solid waste powder passing through a 50-mesh sieve;
(2)高速混合：将纤维质固废物粉末、酯化剂乙醇酸及助剂AlCl3按100：35：7的比例加入到混合机混合均匀，得到混合物；(2) High-speed mixing: Add the fibrous solid waste powder, the esterification agent glycolic acid and the auxiliary agent AlCl3 into the mixer in a ratio of 100:35:7 and mix evenly to obtain a mixture;
(3)机械活化固相反应：将上述混合物磨介质堆体积按照100g:500ml的比例加入机械活化固相反应器中，在转速为500rpm和60℃恒温水浴温度下进行球磨反应，达到1.1h活化时间后，停止搅拌，取出酯化产物和磨球，并将它们分离，得到木质纤维素酯混合物；(3) Mechanically activated solid-phase reaction: add the volume of the above-mentioned mixture into the mechanically activated solid-phase reactor according to the ratio of 100g:500ml, and perform ball milling reaction at a speed of 500rpm and a constant temperature water bath temperature of 60°C to achieve 1.1h activation After a period of time, stop stirring, take out the esterification product and the balls, and separate them to obtain a lignocellulose ester mixture;
(4)后处理：木质纤维素酯混合物进行造粒成球即可得到木质纤维素酯催化剂。(4) Post-treatment: the lignocellulose ester mixture is granulated into balls to obtain the lignocellulose ester catalyst.
实施例8Example 8
木质纤维素酯催化剂的制备，该制备方法包括以下步骤：The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1)原料预处理：将甘蔗渣、木薯酒糟混合的纤维质固废物干燥至含水量小于10％、粉碎得到过60目筛的纤维质固废物粉末；(1) raw material pretreatment: dry the fibrous solid waste mixed with bagasse and cassava distiller's grains until the water content is less than 10%, and pulverize to obtain the fibrous solid waste powder passing through a 60-mesh sieve;
(2)高速混合：将纤维质固废物粉末、酯化剂正辛酸及助剂Al(NO3)3按100：40：8的比例加入到混合机混合均匀，得到混合物；(2) High-speed mixing: Add fibrous solid waste powder, esterifying agent n-octanoic acid and auxiliary agent Al(NO 3 ) 3 into the mixer in a ratio of 100:40:8 and mix evenly to obtain a mixture;
(3)机械活化固相反应：将上述混合物磨介质堆体积按照100g:550ml的比例加入机械活化固相反应器中，在转速为550rpm和38℃恒温水浴温度下进行球磨反应，达到1.2h活化时间后，停止搅拌，取出酯化产物和磨球，并将它们分离，得到木质纤维素酯混合物；(3) Mechanically activated solid-phase reaction: add the volume of the above-mentioned mixture into the mechanically activated solid-phase reactor according to the ratio of 100g:550ml, and perform ball milling reaction at a speed of 550rpm and a constant temperature water bath temperature of 38°C to achieve 1.2h activation After a period of time, stop stirring, take out the esterification product and the balls, and separate them to obtain a lignocellulose ester mixture;
(4)后处理：木质纤维素酯混合物进行造粒成球即可得到木质纤维素酯催化剂。(4) Post-treatment: the lignocellulose ester mixture is granulated into balls to obtain the lignocellulose ester catalyst.
实施例9Example 9
木质纤维素酯催化剂的制备，该制备方法包括以下步骤：The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1)原料预处理：将木薯杆、秸秆、桑枝混合的纤维质固废物干燥至含水量小于15％、粉碎得到过40目筛的纤维质固废物粉末；(1) Raw material pretreatment: dry the fibrous solid waste mixed with cassava stalks, straws and mulberry branches until the water content is less than 15%, and pulverize to obtain the fibrous solid waste powder passing through a 40-mesh sieve;
(2)高速混合：将纤维质固废物粉末、酯化剂月桂酸及助剂Al2(SO4)3按100：20：2的比例加入到混合机混合均匀，得到混合物；(2) High-speed mixing: Add fibrous solid waste powder, esterification agent lauric acid and auxiliary agent Al 2 (SO4) 3 to the mixer in a ratio of 100:20:2 and mix evenly to obtain a mixture;
(3)机械活化固相反应：将上述混合物磨介质堆体积按照100g:300ml的比例加入机械活化固相反应器中，在转速为300rpm和40℃恒温水浴温度下进行球磨反应，达到1.5h活化时间后，停止搅拌，取出酯化产物和磨球，并将它们分离，得到木质纤维素酯混合物；(3) Mechanically activated solid-phase reaction: add the above-mentioned mixture into the mechanically activated solid-phase reactor according to the ratio of 100g:300ml of the mass of the milling medium, and perform ball milling reaction at a speed of 300rpm and a constant temperature water bath temperature of 40°C to achieve 1.5h activation After a period of time, stop stirring, take out the esterification product and the balls, and separate them to obtain a lignocellulose ester mixture;
(4)后处理：木质纤维素酯混合物进行造粒成球即可得到木质纤维素酯催化剂。(4) Post-treatment: the lignocellulose ester mixture is granulated into balls to obtain the lignocellulose ester catalyst.
实施例10Example 10
一种木质纤维素酯催化处理烷基化废硫酸制备硫酸铝的方法，将质量浓度为90.5％的烷基化废硫酸加入到废硫酸质量的30％的氧化铝中反应，至其pH值为1为反应终点，得到混合液，将混合液过滤得到浸出渣和黑色的反应液；然后在反应液中加入实施例1所制备的催化剂木质纤维素酯和氧化剂(双氧水)，催化剂和氧化剂加入的质量分别为废硫酸质量的0.2％和20％，在反应温度在30℃条件下发生氧化还原反应，反应时间30min，即可将烷基化废硫酸中的有机物完全转化为CO2、H2O、N2等无害小分子物质，固液分离，得到纤维质滤渣和清澈透明的精制液，最后将精制液结晶、离心分离、干燥后即可得到纯度可达工业级或饲料级的硫酸铝产品，产品洁白、无刺激性气味。浸出渣和纤维质滤渣混合后进行有机堆肥得到可降解的有机肥基料。A method for preparing aluminum sulfate by catalytically treating alkylated waste sulfuric acid with lignocellulose esters, adding the alkylated waste sulfuric acid with a mass concentration of 90.5% to alumina with a mass concentration of 30% of the waste sulfuric acid to react until the pH value is 1 is the end point of the reaction to obtain the mixed solution, and the mixed solution is filtered to obtain leaching slag and black reaction solution; then the catalyst lignocellulose ester prepared in Example 1 and oxidant (hydrogen peroxide) are added to the reaction solution, and the catalyst and oxidant are added The mass is 0.2% and 20% of the mass of waste sulfuric acid, and the redox reaction occurs at the reaction temperature of 30°C. The reaction time is 30 minutes, and the organic matter in the alkylation waste sulfuric acid can be completely converted into CO 2 and H 2 O , N 2 and other harmless small molecular substances, solid-liquid separation to obtain fibrous filter residue and clear and transparent refined liquid, and finally crystallize the refined liquid, centrifuge and dry to obtain aluminum sulfate with a purity of up to industrial grade or feed grade Product, the product is white and has no irritating smell. The leaching residue and the fibrous filter residue are mixed and organically composted to obtain a degradable organic fertilizer base material.
实施例11Example 11
一种木质纤维素酯催化处理烷基化废硫酸制备硫酸铝的方法，将91％的烷基化废硫酸加入到废硫酸质量的45％的氢氧化铝中反应，至其pH值为1.2为反应终点，得到混合液，将混合液过滤得到浸出渣和黑色的反应液；然后在反应液中加入实施例2所制备的催化剂木质纤维素酯和氧化剂(空气)，催化剂和氧化剂加入的质量分别为废硫酸质量的0.5％和18％，在反应温度在35℃条件下发生氧化还原反应，反应时间50min，即可将烷基化废硫酸中的有机物完全转化为CO2、H2O、N2等无害小分子物质，固液分离，得到纤维质滤渣和清澈透明的精制液，最后将精制液结晶、离心分离、干燥后即可得到纯度可达工业级或饲料级的硫酸铝产品，产品洁白、无刺激性气味。浸出渣和纤维质滤渣混合后进行有机堆肥得到可降解的有机肥基料。A method for preparing aluminum sulfate by catalytically treating alkylated waste sulfuric acid with lignocellulose esters, adding 91% of the alkylated waste sulfuric acid to aluminum hydroxide of 45% of the waste sulfuric acid mass to react until the pH value is 1.2 At the end of the reaction, a mixed solution is obtained, and the mixed solution is filtered to obtain a leaching residue and a black reaction solution; then the catalyst lignocellulose ester and oxidant (air) prepared in Example 2 are added to the reaction solution, and the amounts of the catalyst and oxidant added are respectively 0.5% and 18% of the mass of waste sulfuric acid, redox reaction occurs at the reaction temperature of 35°C, and the reaction time is 50 minutes, the organic matter in the alkylation waste sulfuric acid can be completely converted into CO 2 , H 2 O, N 2 and other harmless small molecular substances, solid-liquid separation, fibrous filter residue and clear and transparent refined liquid are obtained, and finally the refined liquid is crystallized, centrifuged and dried to obtain aluminum sulfate products with a purity of industrial grade or feed grade. The product is white and has no irritating smell. The leaching residue and the fibrous filter residue are mixed and organically composted to obtain a degradable organic fertilizer base material.
实施例12Example 12
一种木质纤维素酯催化处理烷基化废硫酸制备硫酸铝的方法，将91.5％的烷基化废硫酸加入到废硫酸质量的32％的氧化铝中反应，至其pH值为1.4为反应终点，得到混合液，将混合液过滤得到浸出渣和黑色的反应液；然后在反应液中加入实施例3所制备的催化剂木质纤维素酯和氧化剂(氧气)，催化剂和氧化剂加入的质量分别为废硫酸质量的1％和16％，在反应温度在40℃条件下发生氧化还原反应，反应时间70min，即可将烷基化废硫酸中的有机物完全转化为CO2、H2O、N2等无害小分子物质，固液分离，得到纤维质滤渣和清澈透明的精制液，最后将精制液结晶、离心分离、干燥后即可得到纯度可达工业级或饲料级的硫酸铝产品，产品洁白、无刺激性气味。浸出渣和纤维质滤渣混合后进行有机堆肥得到可降解的有机肥基料。A method for preparing aluminum sulfate by catalytically treating alkylated waste sulfuric acid with lignocellulose ester, adding 91.5% of alkylated waste sulfuric acid to alumina with 32% of the mass of waste sulfuric acid to react until the pH value is 1.4 At the end point, a mixed solution is obtained, and the mixed solution is filtered to obtain a leaching residue and a black reaction solution; then the catalyst lignocellulose ester and oxidant (oxygen) prepared in Example 3 are added to the reaction solution, and the quality of the catalyst and oxidant added is respectively 1% and 16% of the mass of waste sulfuric acid, redox reaction occurs at the reaction temperature of 40°C, and the reaction time is 70 minutes, the organic matter in the alkylation waste sulfuric acid can be completely converted into CO 2 , H 2 O, N 2 and other harmless small molecular substances, solid-liquid separation to obtain fibrous filter residue and clear and transparent refined liquid, and finally the refined liquid is crystallized, centrifuged, and dried to obtain aluminum sulfate products with a purity of industrial grade or feed grade. Pure white, no irritating smell. The leaching residue and the fibrous filter residue are mixed and organically composted to obtain a degradable organic fertilizer base material.
实施例13Example 13
一种木质纤维素酯催化处理烷基化废硫酸制备硫酸铝的方法，将92％的烷基化废硫酸加入到废硫酸质量的47％的氢氧化铝中反应，至其pH值为1.8为反应终点，得到混合液，将混合液过滤得到浸出渣和黑色的反应液；然后在反应液中加入实施例4所制备的催化剂木质纤维素酯和氧化剂(臭氧)，催化剂和氧化剂加入的质量分别为废硫酸质量的1.5％和14％，在反应温度在45℃条件下发生氧化还原反应，反应时间90min，即可将烷基化废硫酸中的有机物完全转化为CO2、H2O、N2等无害小分子物质，固液分离，得到纤维质滤渣和清澈透明的精制液，最后将精制液结晶、离心分离、干燥后即可得到纯度可达工业级或饲料级的硫酸铝产品，产品洁白、无刺激性气味。浸出渣和纤维质滤渣混合后进行有机堆肥得到可降解的有机肥基料。A method for preparing aluminum sulfate by catalytically treating alkylated waste sulfuric acid with lignocellulose esters, adding 92% of the alkylated waste sulfuric acid to 47% aluminum hydroxide of the waste sulfuric acid mass to react until its pH value is 1.8 At the end of the reaction, a mixed solution is obtained, and the mixed solution is filtered to obtain a leaching residue and a black reaction solution; then the catalyst lignocellulose ester prepared in Example 4 and an oxidizing agent (ozone) are added to the reaction solution, and the amounts of the catalyst and the oxidizing agent added are respectively It is 1.5% and 14% of the mass of waste sulfuric acid, and the redox reaction occurs at the reaction temperature of 45°C. The reaction time is 90 minutes, and the organic matter in the alkylation waste sulfuric acid can be completely converted into CO 2 , H 2 O, N 2 and other harmless small molecular substances, solid-liquid separation, fibrous filter residue and clear and transparent refined liquid are obtained, and finally the refined liquid is crystallized, centrifuged and dried to obtain aluminum sulfate products with a purity of industrial grade or feed grade. The product is white and has no irritating smell. The leaching residue and the fibrous filter residue are mixed and organically composted to obtain a degradable organic fertilizer base material.
实施例14Example 14
一种木质纤维素酯催化处理烷基化废硫酸制备硫酸铝的方法，将92.5％的烷基化废硫酸加入到废硫酸质量的34％的氧化铝中反应，至其pH值为2.2为反应终点，得到混合液，将混合液过滤得到浸出渣和黑色的反应液；然后在反应液中加入实施例5所制备的催化剂木质纤维素酯和氧化剂(双氧水)，催化剂和氧化剂加入的质量分别为废硫酸质量的2％和12％，在反应温度在50℃条件下发生氧化还原反应，反应时间110min，即可将烷基化废硫酸中的有机物完全转化为CO2、H2O、N2等无害小分子物质，固液分离，得到纤维质滤渣和清澈透明的精制液，最后将精制液结晶、离心分离、干燥后即可得到纯度可达工业级或饲料级的硫酸铝产品，产品洁白、无刺激性气味。浸出渣和纤维质滤渣混合后进行有机堆肥得到可降解的有机肥基料。A method for preparing aluminum sulfate by catalytically treating alkylated waste sulfuric acid with lignocellulose ester, adding 92.5% of alkylated waste sulfuric acid to alumina with a mass of 34% of the waste sulfuric acid to react until the pH value is 2.2 At the end point, a mixed solution is obtained, and the mixed solution is filtered to obtain a leaching residue and a black reaction solution; then the catalyst lignocellulose ester prepared in Example 5 and an oxidizing agent (hydrogen peroxide) are added to the reaction solution, and the added quality of the catalyst and the oxidizing agent is respectively 2% and 12% of the mass of waste sulfuric acid, redox reaction occurs at the reaction temperature of 50°C, and the reaction time is 110min, the organic matter in the alkylation waste sulfuric acid can be completely converted into CO 2 , H 2 O, N 2 and other harmless small molecular substances, solid-liquid separation to obtain fibrous filter residue and clear and transparent refined liquid, and finally the refined liquid is crystallized, centrifuged, and dried to obtain aluminum sulfate products with a purity of industrial grade or feed grade. Pure white, no irritating smell. The leaching residue and the fibrous filter residue are mixed and organically composted to obtain a degradable organic fertilizer base material.
实施例15Example 15
一种木质纤维素酯催化处理烷基化废硫酸制备硫酸铝的方法，将93％的烷基化废硫酸加入到废硫酸质量的48％的氢氧化铝中反应，至其pH值为2.6为反应终点，得到混合液，将混合液过滤得到浸出渣和黑色的反应液；然后在反应液中加入实施例6所制备的催化剂木质纤维素酯和氧化剂(空气)，催化剂和氧化剂加入的质量分别为废硫酸质量的3％和10％，在反应温度在60℃条件下发生氧化还原反应，反应时间130min，即可将烷基化废硫酸中的有机物完全转化为CO2、H2O、N2等无害小分子物质，固液分离，得到纤维质滤渣和清澈透明的精制液，最后将精制液结晶、离心分离、干燥后即可得到纯度可达工业级或饲料级的硫酸铝产品，产品洁白、无刺激性气味。浸出渣和纤维质滤渣混合后进行有机堆肥得到可降解的有机肥基料。A method for preparing aluminum sulfate by catalytically treating alkylated waste sulfuric acid with lignocellulose esters, adding 93% of alkylated waste sulfuric acid to aluminum hydroxide of 48% of the waste sulfuric acid mass to react until its pH value is 2.6 At the end of the reaction, a mixed solution is obtained, and the mixed solution is filtered to obtain a leaching residue and a black reaction solution; then the catalyst lignocellulose ester prepared in Example 6 and an oxidizing agent (air) are added to the reaction solution, and the amounts of the catalyst and the oxidizing agent added are respectively 3% and 10% of the mass of waste sulfuric acid, redox reaction occurs at the reaction temperature of 60°C, and the reaction time is 130 minutes, the organic matter in the alkylation waste sulfuric acid can be completely converted into CO 2 , H 2 O, N 2 and other harmless small molecular substances, solid-liquid separation, fibrous filter residue and clear and transparent refined liquid are obtained, and finally the refined liquid is crystallized, centrifuged and dried to obtain aluminum sulfate products with a purity of industrial grade or feed grade. The product is white and has no irritating smell. The leaching residue and the fibrous filter residue are mixed and organically composted to obtain a degradable organic fertilizer base material.
实施例16Example 16
一种木质纤维素酯催化处理烷基化废硫酸制备硫酸铝的方法，将95％的烷基化废硫酸加入到废硫酸质量的50％的氢氧化铝中反应，至其pH值为3.0为反应终点，得到混合液，将混合液过滤得到浸出渣和黑色的反应液；然后在反应液中加入实施例7所制备的催化剂木质纤维素酯和氧化剂(氧气)，催化剂和氧化剂加入的质量分别为废硫酸质量的4％和7％，在反应温度在70℃条件下发生氧化还原反应，反应时间150min，即可将烷基化废硫酸中的有机物完全转化为CO2、H2O、N2等无害小分子物质，固液分离，得到纤维质滤渣和清澈透明的精制液，最后将精制液结晶、离心分离、干燥后即可得到纯度可达工业级或饲料级的硫酸铝产品，产品洁白、无刺激性气味。浸出渣和纤维质滤渣混合后进行有机堆肥得到可降解的有机肥基料。A method for preparing aluminum sulfate by catalytically treating alkylated waste sulfuric acid with lignocellulose esters, adding 95% of the alkylated waste sulfuric acid to 50% aluminum hydroxide of the waste sulfuric acid mass to react until the pH value is 3.0 At the end of the reaction, a mixed solution is obtained, and the mixed solution is filtered to obtain a leaching residue and a black reaction solution; then the catalyst lignocellulose ester prepared in Example 7 and an oxidizing agent (oxygen) are added to the reaction solution, and the amounts of the catalyst and the oxidizing agent added are respectively It is 4% and 7% of the mass of waste sulfuric acid. When the reaction temperature is 70°C, redox reaction occurs, and the reaction time is 150 minutes, and the organic matter in the alkylation waste sulfuric acid can be completely converted into CO 2 , H 2 O, N 2 and other harmless small molecular substances are separated from solid and liquid to obtain fibrous filter residue and clear and transparent refined liquid. Finally, the refined liquid is crystallized, centrifuged and dried to obtain aluminum sulfate products with a purity of industrial grade or feed grade. The product is white and has no irritating smell. The leaching residue and the fibrous filter residue are mixed and organically composted to obtain a degradable organic fertilizer base material.
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