CN108946697A - A kind of processing method using waste sulfuric acid from alkylation production biomass carbon - Google Patents
A kind of processing method using waste sulfuric acid from alkylation production biomass carbon Download PDFInfo
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- CN108946697A CN108946697A CN201810872200.4A CN201810872200A CN108946697A CN 108946697 A CN108946697 A CN 108946697A CN 201810872200 A CN201810872200 A CN 201810872200A CN 108946697 A CN108946697 A CN 108946697A
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- sulfuric acid
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- acid
- biomass carbon
- waste sulfuric
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 239000002028 Biomass Substances 0.000 title claims abstract description 74
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 59
- 239000002699 waste material Substances 0.000 title claims abstract description 40
- 230000029936 alkylation Effects 0.000 title claims abstract description 32
- 238000005804 alkylation reaction Methods 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 15
- 238000003672 processing method Methods 0.000 title claims abstract description 13
- 239000002253 acid Substances 0.000 claims abstract description 54
- 239000003610 charcoal Substances 0.000 claims abstract description 14
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 7
- 230000000694 effects Effects 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 239000000908 ammonium hydroxide Substances 0.000 claims description 5
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 16
- 230000008569 process Effects 0.000 abstract description 8
- 239000002994 raw material Substances 0.000 abstract description 7
- 238000005265 energy consumption Methods 0.000 abstract description 6
- 238000010438 heat treatment Methods 0.000 abstract description 4
- HGUFODBRKLSHSI-UHFFFAOYSA-N 2,3,7,8-tetrachloro-dibenzo-p-dioxin Chemical compound O1C2=CC(Cl)=C(Cl)C=C2OC2=C1C=C(Cl)C(Cl)=C2 HGUFODBRKLSHSI-UHFFFAOYSA-N 0.000 abstract 1
- 239000000706 filtrate Substances 0.000 description 18
- 239000002689 soil Substances 0.000 description 14
- 239000012065 filter cake Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000005416 organic matter Substances 0.000 description 10
- KVGZZAHHUNAVKZ-UHFFFAOYSA-N 1,4-Dioxin Chemical compound O1C=COC=C1 KVGZZAHHUNAVKZ-UHFFFAOYSA-N 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 240000007594 Oryza sativa Species 0.000 description 5
- 235000007164 Oryza sativa Nutrition 0.000 description 5
- 238000003763 carbonization Methods 0.000 description 5
- 239000003337 fertilizer Substances 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 235000009566 rice Nutrition 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 239000010903 husk Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 239000004215 Carbon black (E152) Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229930195733 hydrocarbon Natural products 0.000 description 3
- 150000002430 hydrocarbons Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 240000007049 Juglans regia Species 0.000 description 2
- 235000009496 Juglans regia Nutrition 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- 240000008042 Zea mays Species 0.000 description 2
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 description 2
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 235000005822 corn Nutrition 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000005417 food ingredient Substances 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 235000013324 preserved food Nutrition 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010907 stover Substances 0.000 description 2
- 238000006277 sulfonation reaction Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 239000011593 sulfur Substances 0.000 description 2
- 235000020234 walnut Nutrition 0.000 description 2
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 1
- 241000609240 Ambelania acida Species 0.000 description 1
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 1
- 235000017491 Bambusa tulda Nutrition 0.000 description 1
- 235000021537 Beetroot Nutrition 0.000 description 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Polymers C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 1
- 241000167854 Bourreria succulenta Species 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 241000219146 Gossypium Species 0.000 description 1
- 240000002024 Gossypium herbaceum Species 0.000 description 1
- 235000004341 Gossypium herbaceum Nutrition 0.000 description 1
- 240000003183 Manihot esculenta Species 0.000 description 1
- 235000016735 Manihot esculenta subsp esculenta Nutrition 0.000 description 1
- 240000008790 Musa x paradisiaca Species 0.000 description 1
- 235000018290 Musa x paradisiaca Nutrition 0.000 description 1
- 244000082204 Phyllostachys viridis Species 0.000 description 1
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 1
- 235000021307 Triticum Nutrition 0.000 description 1
- 244000098338 Triticum aestivum Species 0.000 description 1
- 244000126002 Ziziphus vulgaris Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000008065 acid anhydrides Chemical class 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 239000002154 agricultural waste Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical group [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
- 239000010905 bagasse Substances 0.000 description 1
- 239000011425 bamboo Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000019693 cherries Nutrition 0.000 description 1
- 238000005660 chlorination reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000035558 fertility Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 230000002906 microbiologic effect Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 235000016709 nutrition Nutrition 0.000 description 1
- 230000035764 nutrition Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- FWFGVMYFCODZRD-UHFFFAOYSA-N oxidanium;hydrogen sulfate Chemical compound O.OS(O)(=O)=O FWFGVMYFCODZRD-UHFFFAOYSA-N 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000005067 remediation Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000003516 soil conditioner Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 125000000472 sulfonyl group Chemical group *S(*)(=O)=O 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000002912 waste gas Substances 0.000 description 1
- 238000005303 weighing Methods 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
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of processing methods using alkylation spent acid production biomass carbon, belong to field of environment engineering.Biomass is added in alkylation spent acid by the present invention using biomass as raw material, and heating makes the polymerization charing under effect of sulfuric acid of the molten oil of the acid in biomass and Waste Sulfuric Acid obtain biomass carbon.The biomass carbon yield that this method obtains is greater than 60%, and no dioxin significantly reduces charcoal discharge, reduces energy consumption, realize the inexpensive charing process of biomass, meets Green Chemistry requirement.
Description
Technical field
The present invention relates to a kind of processing methods using waste sulfuric acid from alkylation production biomass carbon, belong to environmental project neck
Domain.
Technical background:
Waste Sulfuric Acid results from the production process of the fine chemical products such as nitrification, sulfonation, alkylation, the esterification of organic matter,
Mineral products processing, petroleum refining, national defense industry etc. are arisen in, the Waste Sulfuric Acid generated in production process is always to perplex manufacturing enterprise
A great problem.Country's sulfuric acid process alkylation production capacity is more than 15,000,000 tons at present, such as will have 1,500,000 tons or more of sulfur waste up to production
Acid.The molten oil of acid rouge, acid and water account for about 10-15% or so in waste sulfuric acid from alkylation, and appearance is brown or dark brown and has strong
Strong penetrating odor.It is domestic big if executed in strict accordance with the environmental protection policy and regulation on Management of Drug-Making Chemicals of country
The enterprise that majority generates Waste Sulfuric Acid will shut down.Since Waste Sulfuric Acid is a kind of liquid, row steals and puts to come than solid waste and exhaust gas steathily
It is convenient and hidden, it therefore, is said from the angle of environmental protection, the improvement of Waste Sulfuric Acid is just extremely urgent.
The molten oil of acid in waste sulfuric acid from alkylation becomes the difficult point that sulfuric acid is administered, and industry at present is commonly high temperature pyrolytic cracking (HTP),
The organic matters such as the molten oil of the acid generation carbon dioxide that burn at high temperature is discharged into atmosphere, and other methods are difficult to promote due to economy
Using.Increasingly strict with environmental requirement, low cost, the processing of recycling sulfuric acid alkylation spent acid are imperative.It is Chinese special
Sharp CN201610682877.2 and CN201710946286.5 propose the molten oil of acid in alkylation spent acid be height it is unsaturated and from
The complex mixture of sonization, using the unsaturated double-bond and hydrogen bond of these molten hydrocarbon molecules of acid, intensified acid is molten in strong acidic environment
The reaction such as esterification, sulfonation, polymerization, charing of oil, is allowed to generate the charcoal base acid material containing groups such as sulfuryl, sulfonic groups, and
Realize the separation of acid molten oil and sulfuric acid.Thus environmental pollution can not only be mitigated significantly by carrying out resource utilization to Waste Sulfuric Acid, but also can be returned
A part of sulfuric acid resource and carbon resource are received, lower reaction temperature significantly reduces recycling energy consumption, has great economy
Benefit and environmental benefit.
Biomass carbon (Biochar), also referred to as charcoal, biological carbon, biomass carbon, biomass char etc..As a kind of soil
Earth modifying agent, charcoal forms the soil carbon combination of an indomitable carbon negativity, and carbon dioxide storage in atmosphere is arrived
In the carbon base in soil of highly resistant.After applied charcoal in soil, the enhancing of nutrition persistence not only reduces crop to fertilizer
The demand of material, and the influence certain for weather and environment.
The raw material sources of charcoal are very extensive, according to the literature, many agriculture and forestry by-products, for example, jujube core, walnut shell,
Walnut shell, useless tealeaves, corncob, cocoanut shell, beet root, peanut shell, rice hulls, levant cotton exocarp, banana skin, bamboo waste, dento liva,
Cherry stone, orange peel, coffee beanpod, corn stover and cassava skin etc. are tried the charcoal for being used to prepare low cost.Due to
For carbon atom to each other with the combination of extremely strong affinity, charcoal has very high chemistry and biology stability, and soluble pole
It is low.These fundamental propertys of charcoal make it have absorption property, catalytic performance and antibiont capacity of decomposition, agricultural, the energy,
The fields such as environment are all widely used.
The influence of biomass carbon includes improving soil texture, improves aggregate stability, improves soil water capacity, is promoted micro-
Biological growth, and finally improve the productivity (10%) of soil.While improving crop yield, biomass carbon can also be quick
Soil organic carbon is improved, N2O discharge amount and Heavy Metals in Soil Contaminated biological effectiveness are reduced.Soil improvement and upgrading are imitated
It answers, especially carbon fixation and emission reduction is still current protrusion demand.Waste charing has not only handled the wastes such as stalk, avoids
The directly discharge of burning or heap buried decomposition, increases soil organism carbon storehouse, also significantly improves the physical property of soil, promotees
It into biological growth and activity, improves fertility and reduces risk of environmental pollution, be the important channel of soil sustainable management.
The agricultural wastes such as stalk are not utilized effectively, and a large amount of directly burn exacerbates atmosphere pollution.In national green development strategy
Under frame, the outlet of the sustainable management of soil and changing rejected material to useful resource circulation as complementary agricultural sustainable development.
Preparing the most common method of charcoal is pyrolysis method, i.e., thermally decomposes in no oxygen or oxygen-limited condition environment
Organic material, the solid matter of formation, main component are carbon, hydrogen, oxygen, nitrogen etc., also include a small amount of microelement, carbon containing
Amount is generally 60% or more.In carbonization process, non-carbon element is decomposed and evolution forms hole configurations, therefore has certain hole
Porosity and specific surface area.Charcoal surface functional group very abundant includes a variety of groups such as carboxyl, phenolic hydroxyl group, acid anhydrides.Pyrolysismethod
Handle biomass adaptability it is relatively preferable, in terms of process performance index also have some superiority, decrement than reach 95% with
On, and auxiliary fuel, recoverable energy are not needed in operation, waste is not required to classify and pre-process.But waste gas from incinerator processing dress
It is serious to set acidification, dioxin cannot be guaranteed that stably reaching standard discharges, and overhaul costly.And the control for dioxin, it is biomass
Burn problem the most intractable.Since dioxin generting machanism is considerably complicated, according to domestic literature, it is known that constructive ways conclude 2
A aspect: 1) predecessor heterogeneous catalytic reaction forms dioxin.That is the organic compounds such as polystream, chlorophenols, PVC, in metal
At catalyst (copper chloride, iron chloride etc.) and 450~700 DEG C, reacts and generate dioxin；2) it recombines reaction and forms two
English is disliked, i.e., (coke flies for imperfect combustion particulate organic carbon (propylene, toluene, chlorobenzene etc.) and giant molecule carbon structure in flying dust
Ash, residual carbon etc.) at 250~850 DEG C, by different catalyst, aoxidized, chlorination, polymerization form dioxin.So
The optimum synthesising temperature of dioxin is 250~400 DEG C.
Sulfuric acid charring is at a lower temperature to be taken off carbon containing biomass material using the dehydration property and highly acid of the concentrated sulfuric acid
Water charing, obtains the process of biomass carbon material.CN103157509, CN103157512 disclose the concentrated sulfuric acid and bagasse (or
Rice husk) Hybrid Heating is partially carbonized prepares solid sulfoacid, and CN100421793, CN100421792 are disclosed with plant material or carbon
The method that hydrate prepares solid sulfoacid, but be carbonized not exclusively, solid carbon yield is low, and Organic Materials of Spent acid content is high.Once
There are research sulfuric acid catalysis charing sludge and cotton, but degree of carbonization is low, the carbide granularity for needing to carbonize and generate twice
It is small, it is soluble in sulfuric acid, is difficult to separate, wash high organic content in acid, can not comprehensively utilize.Therefore, develop it is a kind of it is low at
Originally, the recycling processing method of innoxious biomass, has great importance.
Summary of the invention
For the technical problems in the prior art, the present invention provides a kind of waste sulfuric acid from alkylation to produce biomass carbon
The processing method of change.
The molten hydrocarbon of acid contained in waste sulfuric acid from alkylation is the complex mixture that height is unsaturated and ionizes, biomass material
Short texture, distribution dispersion, occupied space are big.A large amount of foam can be generated in waste sulfuric acid from alkylation heating polymerization process, and is given birth to
The molecule of these easy bubbles just can be absorbed in the loose structure of substance, improves the carbonization degree of the molten oil of acid in alkylation spent acid.
Using the unsaturated double-bond and hydrogen bond of these molten hydrocarbon molecules of acid, by the effect of sulfuric acid, biomass is in strong acidic environment neutralizing acid
The reactions such as the raw polymerization of molten fry dried food ingredients, charing are carbonized completely, are reacted the organic matter in biomass and spent acid and are generated resourcebility benefit
Biomass carbon.
The present invention realizes the resource utilization benefit of organic matter in biomass and waste sulfuric acid from alkylation using biomass as raw material
With reducing carbon emission, obtained biomass carbon and diluted acid have biggish application value.The processing method reaction step is few,
Energy consumption is low, realizes the charing process of low-cost bio matter, applied widely, meets Green Chemistry requirement.Biomass
Carbonizing treatment method includes the following steps that be heated to biomass after (1) mixes biomass with waste sulfuric acid from alkylation carbonizes completely,
Obtain mixture；(2) mixture that step (1) generates is down to room temperature, solvent is added into mixture, stirring is adsorbed into charcoal
Acid all dissolve out, washing, drying obtain biomass carbon and diluted acid.
The weight ratio of waste sulfuric acid from alkylation and biomass is 0.1~10:1.
The temperature of heating reaction is 100~300 DEG C in step (1), and the time is 0.5~4 hour.
Solvent is water, dilute sulfuric acid, phosphoric acid,diluted or ammonium hydroxide, sig water in step (2)；The additional amount of solvent is sulfuric acid weight
1~10 times, preferably 1~5 times.Dilute sulfuric acid, phosphoric acid,diluted refer to mass percentage in 30% acid below.
Available dilute sulfuric acid or sulfate and biomass carbon after washing, biomass carbon and with sulfate compositions be biology
Matter charcoal fertilizer, or as the raw material of biomass carbon fertilizer.
The temperature dried in step (2) is 60~200 DEG C；The pressure of drying is -0.1~0.1MPa；The time of drying is
0.5~4 hour；The number of washing is 1~6 time.
The present invention realizes the resource utilization of organic matter and acid in biomass and waste sulfuric acid from alkylation using biomass as raw material
It utilizes, reduces carbon emission, obtained biomass carbon and diluted acid have biggish application value；Reduce reaction step, reduce
Energy consumption, Biomass are biomass carbon, high conversion rate.Due to being provided to biomass and the organic Waste Sulfuric Acid of high concentration
Sourceization utilizes can not only mitigate environmental pollution significantly, but also a part of sulfuric acid resource and carbon resource can be recycled, and lower reaction temperature
It significantly reduces recycling energy consumption, without dioxin in discharge gas, there is great economic benefit and environmental benefit.The present invention
The method route of offer is short, easy to operate, low energy consumption, applied widely, meets Green Chemistry requirement.
The beneficial effects of the present invention are:
In the present invention, it is heated after biomass mixed alkyl Waste Sulfuric Acid, the molten fry dried food ingredients of acid in biomass and Waste Sulfuric Acid is raw
The reactions such as polymerization, charing generate biomass carbon, improve the carbonization yield of the molten oil of acid, without dioxin in discharge gas, at reduction
Content of organics in diluted acid after reason.Product is washed by solution after reaction realizes that Carbon Materials are separated with acid, respectively obtains biomass carbon
And diluted acid, it can be using synthesis materials such as chemical fertilizer, bodied ferric sulfates.Biomass carbonated obtained biomass carbon has raw material sources
Abundant, cheap, large specific surface area, pore structure prosperity, thermal stability and good chemical stability, can answer extensively
For various fields such as agricultural, environment remediation, chemical industry, energy storages, as biomass carbon fertilizer and soil conditioner, useless underwater gold
Category or the adsorbent of organic matter, the adsorbent of atmosphere pollution, acid catalyst or catalyst carrier, electrode and super capacitor material
Deng having broad application prospects.
Specific embodiment
The technical scheme of the invention is further explained by means of specific implementation.Those skilled in the art should be bright
, the described embodiments are merely helpful in understanding the present invention, should not be regarded as a specific limitation of the invention.
Embodiment 1
Weigh waste sulfuric acid from alkylation 102.5g (acid concentration 89.2% contains organic matter 6.8%) in a round bottom flask
(250mL) is added the rice husk of spent acid quality 20%, is increased to 160 DEG C from room temperature, then maintains 3.5h, be cooled to room temperature, weigh
The water that 1 times of spent acid quality is added in round-bottomed flask, stirs 30min, and water re-using washing, stirring 3 times obtain filtrate (dilute sulphur
Acid solution) and filter cake (biomass carbon), filtrate is collected into beaker, and the COD value of filtrates tested is 469.7mg/L, in stirring
Under the conditions of be slowly added into ammonium hydroxide (25~28wt%) until solution is in neutrality, then evaporate solution to there is ammonia sulfate crystal precipitation.
Filter cake is washed with deionized until neutrality, dries 2 hours at 100 DEG C, 0.1MPa, obtain biomass carbon 21.96g.
Embodiment 2
Weigh waste sulfuric acid from alkylation 103.4g (acid concentration 89.2% contains organic matter 6.8%) in a round bottom flask
(250mL) is added the sawdust of spent acid quality 40%, is increased to 220 DEG C from room temperature, then maintains 3h, be cooled to room temperature, weigh useless
The water of 1 times of sour quality is added in round-bottomed flask, stirs 30min, and water re-using washing, stirring 3 times obtain filtrate (dilute sulfuric acid
Solution) and filter cake (Carbon Materials), filtrate is collected into beaker, and the COD value of filtrates tested is 361.7mg/L, in the condition of stirring
Under be slowly added into ammonium hydroxide (25~28wt%) until solution is in neutrality, then evaporate solution to there is crystal precipitation.Use deionized water
Filter cake is washed until neutrality, dries 3 hours at 150 DEG C, 0.05MPa, obtain biomass carbon 38.72g.
Embodiment 3
Weigh waste sulfuric acid from alkylation 102.9g (acid concentration 89.2% contains organic matter 6.8%) in a round bottom flask
(250mL) is added 1 times of spent acid quality of rice husk, is increased to 220 DEG C from room temperature, then maintains 2h, be cooled to room temperature, weigh sulphur
The water of 1 times of sour quality is added in round-bottomed flask, stirs 30min, and water re-using washing, stirring 3 times obtain filtrate (dilute sulfuric acid
Solution) and filter cake (Carbon Materials), filtrate is collected into beaker, the COD value 634.9mg/L of filtrates tested, under stirring conditions
Ammonium hydroxide (25~28wt%) is slowly added into until solution is in neutrality, then evaporates solution to there is crystal precipitation.It is washed with deionized water
Filter cake is washed until neutrality, dries 3 hours at 200 DEG C, 0.01MPa, obtain biomass carbon 87.9g.
Embodiment 4
Weigh waste sulfuric acid from alkylation 101.5g (acid concentration 89.2% contains organic matter 6.8%) in a round bottom flask
(250mL) is added the corn stover of spent acid quality 10%, is increased to 240 DEG C from room temperature, then maintains 1h, be cooled to room temperature, claim
The water for taking spent acid quality equal is added in round-bottomed flask, stirs 30min, and it is (dilute to obtain filtrate for water re-using washing, stirring 3 times
Sulfuric acid solution) and filter cake (Carbon Materials), filtrate is collected into beaker, the COD value 867.9mg/L of filtrates tested.Use deionized water
Filter cake is washed until neutrality, dries 4 hours at 100 DEG C, 0.1MPa, obtain biomass carbon 12.5g.
Embodiment 5
Weigh waste sulfuric acid from alkylation 103.8g (acid concentration 89.2% contains organic matter 6.8%) in a round bottom flask
(250mL) is added the wheat stalk of spent acid quality 10%, is increased to 160 DEG C from room temperature, then maintains 3.5h, be cooled to room temperature,
The water for weighing spent acid quality 150% is added in round-bottomed flask, stirs 30min, is washed repeatedly 2 times, obtaining filtrate, (dilute sulfuric acid is molten
Liquid) and filter cake (Carbon Materials), filtrate is collected into beaker, the COD value 1591.4mg/L of filtrates tested.Filter is washed with deionized
Cake dries 2 hours at 100 DEG C, 0.1MPa until neutrality, obtains biomass carbon 12.5g.
Comparative example
It weighs sulfuric acid 102.7g (250mL) in a round bottom flask, the rice husk of sulfuric acid quality 50% is added, is increased to from room temperature
200 DEG C, 3.5h is then maintained, is cooled to room temperature, 1 times of sulfuric acid quality of water is weighed and is added in round-bottomed flask, stirs 30min,
Water re-using washing, stirring 3 times, obtain filtrate (dilution heat of sulfuric acid) and filter cake (Carbon Materials), collect filtrate into beaker, test
The COD value 3524.8mg/L of filtrate.Filter cake is washed with deionized until neutrality, dries 2 hours at 100 DEG C, 0.1MPa, obtain
To biomass carbon 32.9g.
As it can be seen that waste sulfuric acid from alkylation and biomass Co-carbonization reaction efficiency ratio using bright sulfur acid with it is biomass carbonated high,
Reaction process is mild, biomass carbon high income, and content of organics is few in dilution heat of sulfuric acid.
The Applicant declares that a kind of charing process side of the present invention is explained by the above embodiments biomass of the invention
Method, but the invention is not limited to above-mentioned processing steps, that is, it is real not mean that the present invention must rely on above-mentioned processing step ability
It applies.It should be clear to those skilled in the art, any improvement in the present invention, to the equivalent of raw material selected by the present invention
Replacement and addition, the selection of concrete mode of auxiliary element etc., all of which fall within the scope of protection and disclosure of the present invention.
Claims (6)
1. a kind of processing method using waste sulfuric acid from alkylation production biomass carbon, it is characterised in that: biomass is added to alkane
In base spent acid, it is heated to the molten oily polymerization charing under effect of sulfuric acid of acid that 100~300 DEG C make in biomass and Waste Sulfuric Acid and obtains
Biomass carbon.The following steps are included:
(1) biomass is dry, crush as powdered biomass；
(2) it is heated to 100~300 DEG C after mixing with waste sulfuric acid from alkylation to carbonize biomass completely, obtains mixture；
(3) mixture that step (2) generate is down to room temperature, solvent is added into mixture, it is complete to stir the acid adsorbed into charcoal
Portion dissolve out, washing, drying obtain biomass carbon and diluted acid.
2. a kind of processing method using waste sulfuric acid from alkylation production biomass carbon according to claim 1, feature exist
In: the weight ratio of sulfuric acid described in step (2) and biomass is 0.1~10:1.
3. a kind of processing method using waste sulfuric acid from alkylation production biomass carbon according to claim 1, feature exist
In: the temperature that reaction is heated described in step (1) is 160~250 DEG C, and the time is 0.5~4 hour.
4. a kind of processing method using waste sulfuric acid from alkylation production biomass carbon according to claim 1, feature exist
In: solvent described in step (2) is water, the dilute sulfuric acid of concentration 1%~50%, the phosphoric acid,diluted of concentration 1%~30% or concentration 1%
~30% ammonium hydroxide；The additional amount of solvent is 1~10 times of sulfuric acid weight.
5. a kind of processing method using waste sulfuric acid from alkylation production biomass carbon according to claim 1, feature exist
In: the additional amount of solvent is 1~5 times of sulfuric acid weight.
6. a kind of processing method using waste sulfuric acid from alkylation production biomass carbon according to claim 1, feature exist
In: the temperature dried in step (2) is 60~200 DEG C；The pressure of drying is -0.1~0.1MPa；The time of drying is 0.5~4
Hour；The number of washing is 1~6 time.
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Cited By (6)
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| CN110550610A (en) * | 2019-10-18 | 2019-12-10 | 斯瑞尔环境科技股份有限公司 | Regeneration treatment method of alkylation waste sulfuric acid |
| CN111333905A (en) * | 2020-04-20 | 2020-06-26 | 中国科学院过程工程研究所 | Recovery method of fiber reinforced composite material |
| CN111533584A (en) * | 2020-06-12 | 2020-08-14 | 山东鲁北化工股份有限公司 | Preparation method of biomass sulfonated carbon based diammonium phosphate |
| CN111646856A (en) * | 2020-06-12 | 2020-09-11 | 山东鲁北化工股份有限公司 | Preparation method of biomass sulfonated carbon-based compound fertilizer |
| CN112897503A (en) * | 2021-01-25 | 2021-06-04 | 上海应用技术大学 | Acid modification preparation method of biomass charcoal material with toluene adsorption effect |
| CN113415803A (en) * | 2021-08-12 | 2021-09-21 | 中国科学院生态环境研究中心 | Waste treatment method |
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| CN105000558A (en) * | 2015-08-14 | 2015-10-28 | 赵常然 | Method for directly preparing activated carbon in waste acid |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110550610A (en) * | 2019-10-18 | 2019-12-10 | 斯瑞尔环境科技股份有限公司 | Regeneration treatment method of alkylation waste sulfuric acid |
| CN111333905A (en) * | 2020-04-20 | 2020-06-26 | 中国科学院过程工程研究所 | Recovery method of fiber reinforced composite material |
| CN111533584A (en) * | 2020-06-12 | 2020-08-14 | 山东鲁北化工股份有限公司 | Preparation method of biomass sulfonated carbon based diammonium phosphate |
| CN111646856A (en) * | 2020-06-12 | 2020-09-11 | 山东鲁北化工股份有限公司 | Preparation method of biomass sulfonated carbon-based compound fertilizer |
| CN112897503A (en) * | 2021-01-25 | 2021-06-04 | 上海应用技术大学 | Acid modification preparation method of biomass charcoal material with toluene adsorption effect |
| CN113415803A (en) * | 2021-08-12 | 2021-09-21 | 中国科学院生态环境研究中心 | Waste treatment method |
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