CN105502309A - Method for catalyzing alkylated waste sulfuric acid through lignocellulose ester - Google Patents
Method for catalyzing alkylated waste sulfuric acid through lignocellulose ester Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B17/00—Sulfur; Compounds thereof
- C01B17/96—Methods for the preparation of sulfates in general
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- 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
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- C—CHEMISTRY; METALLURGY
- C05—FERTILISERS; MANUFACTURE THEREOF
- C05F—ORGANIC FERTILISERS NOT COVERED BY SUBCLASSES C05B, C05C, e.g. FERTILISERS FROM WASTE OR REFUSE
- C05F7/00—Fertilisers from waste water, sewage sludge, sea slime, ooze or similar masses
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02A40/00—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production
- Y02A40/10—Adaptation technologies in agriculture, forestry, livestock or agroalimentary production in agriculture
- Y02A40/20—Fertilizers of biological origin, e.g. guano or fertilizers made from animal corpses
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Abstract
Provided is a method for catalyzing alkylated waste sulfuric acid through lignocellulose ester. The method comprises the steps that the alkylated waste sulfuric acid is added to metallic oxide or hydroxide to react till the pH value is weak acidic, then catalyst lignocellulose ester and an oxidizing agent are added for a redox reaction, and organic matter in the alkylated waste sulfuric acid is converted into CO2, H2O, N2 and other harmless micromolecular matter. Obtained reaction liquid generated after oxydative degradation and decoloration is refined to be prepared into inorganic salt. Selected lignocellulose ester has a catalyzing function, and has the functions of activating the oxidizing agent and achieving adsorption decoloration. Other impurities are not introduced in the production process, secondary pollution cannot be caused, the organic matter in the waste acid is oxidized to be degraded, all mother liquor is cyclically utilized, and product quality cannot be influenced, and reaches the quality standard of the feed grade and the industrial grade. The production process is easy to operate, safe and reliable, operation is carried out at normal pressure, and investment is reduced. The lignocellulose ester catalyst can be biodegraded, and can serve as a raw material of biofertilizer, and no three wastes are discharged in the production process.
Description
Technical field
The invention belongs to treatment of Organic Wastewater field, specifically a kind of lignocellulose ester is applied to the method for process waste sulfuric acid from alkylation as oxide catalyst.
Background technology
Along with the world is to the raising of fuel demand, current refinery extensively adopts alkylation process to produce octane-iso, and output rapidly increases.During gasoline alkylate high-octane with alkyl plant processing, need be that the sulfuric acid of 98% is as catalyzer by concentration, often produce 1 ton of gasoline alkylate and just produce 80 ~ 100kg Waste Sulfuric Acid, containing sulfuric acid, the organism of about 7% and the water of about 3% of about 90% in Waste Sulfuric Acid.Organism is polymer alkene, diolefine, alkylsulphonic acid, sulfuric ester and sulfide etc. mainly, and these material colors are dark, quality thickness, Odor stimulation, is difficult to thoroughly remove from sulfuric acid.Existing ripe treatment technology mainly pyrolysis recycle becomes sulfuric acid reuse, but facility investment is huge, and process Waste Sulfuric Acid per ton costly, lose huge, this brings great pressure to the cost of manufacturing enterprise and environment, is the biggest problem that puzzlement enterprise produces.Other have the treatment process such as extraction, but extraction solvent cost recovery is high, sulfuric acid content is low, there is not yet the enterprise of application.In addition, utilize waste sulfuric acid from alkylation to produce ammonium sulfate, magnesium sulfate, atlapulgite, precipitated silica, oil rust-preventive agent etc. and also have research, but due to the organism removed in Waste Sulfuric Acid of can not effectively degrading, product has stronger irritating smell, be difficult to obtain highly purified product, and the treatment agent added easily causes secondary pollution, mother liquor is difficult to recycle.Therefore, current waste sulfuric acid from alkylation still can not get effective process, overstocks in a large number in manufacturing enterprise, and make enterprise face the risk of stopping production, this brings huge financial loss by enterprise.
Chinese patent title: a kind of renovation process of waste sulfuric acid from alkylation; Application Number (patent): CN201210410373.7; The applying date: 2012.10.24; Open (bulletin) number: CN103771353A; Open (bulletin) day: 2014.05.07; A kind of renovation process of waste sulfuric acid from alkylation of this disclosure of the invention, comprise: under Redox Condition, Waste Sulfuric Acid contacts with oxidation promoter, the organism in Waste Sulfuric Acid or small carbon granule and oxidant reaction obtain being converted into CO2, N2, H2O, after stripping removes, obtain the sulfuric acid after regenerating.The method of regeneration waste sulfuric acid from alkylation provided by the invention is carried out under lower pressure and temperature, and plant running energy consumption is low, reduces investment outlay, simple to operate, and device maintenance cost is low.Principal claim: a kind of renovation process of waste sulfuric acid from alkylation, is characterized in that, under Redox Condition, Waste Sulfuric Acid contacts with oxidation promoter, organism in Waste Sulfuric Acid or small carbon granule and oxidant reaction obtain being converted into CO2, N2, H2O, after stripping removes, obtain the sulfuric acid after regenerating.But fully effective degraded can not remove organism in Waste Sulfuric Acid, can not realize degradable.
Summary of the invention
For above-mentioned Problems existing, this invention exploits a kind of method of waste sulfuric acid from alkylation process, the waste residue after the method process, reaction solution all have no irritating odor, and reaction solution is as clear as crystal.Reaction solution can be used for producing inorganic salt after treatment, and the waste residue after handled may be used for producing fertilizer.
Concrete technical scheme of the present invention is as follows:
A kind of method of lignocellulose ester catalysis process waste sulfuric acid from alkylation, react joining in waste sulfuric acid from alkylation in metal oxide or oxyhydroxide, be slightly acidic to its pH value, then adding catalyzer lignocellulose ester and oxygenant generation redox reaction, is CO by the organism in waste sulfuric acid from alkylation by deep oxidation Degradation and Transformation
2, H
2o, N
2etc. harmless small-molecule substance.In order to fully realize utilization of waste material, filtered while hot, filtrate produces inorganic salt product through refining, and product reaches the requirement of technical grade, and product reaches the requirement of technical grade; The whole recycle of mother liquor; Filter residue is cellulosic materials, can be used as the raw material of bio-feritlizer.
The method of above-described lignocellulose ester catalysis process waste sulfuric acid from alkylation, described lignocellulose ester preparation method comprises the following steps:
(1) raw materials pretreatment: cellulosic solid waste is dry, pulverizing obtains cellulosic solid waste powder;
(2) high-speed mixing: join mixing machine in the ratio of cellulosic solid waste powder, esterifying agent and auxiliary agent 100:5-40:1-8 and mix, obtain mixture;
(3) mechanical activation solid state reaction: said mixture grinding media heap volume is added in mechanical activation solid phase reactor according to the ratio of 100g:200-600ml, ball-milling reaction is carried out under rotating speed is 200-600rpm and 30-60 DEG C of water bath with thermostatic control temperature, after reaching 0.5-1.5h soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulose ester mixture;
(4) aftertreatment: lignocellulose ester mixture carries out granulation balling-up can obtain lignocellulose ester catalyst.
The method of above-described lignocellulose ester catalysis process waste sulfuric acid from alkylation, described esterifying agent is carboxylic acid, described carboxylic acid comprises succsinic acid, toxilic acid, oxalic acid, citric acid, butyric acid, oxyacetic acid, amino acid, n-caprylic acid, lauric acid any or two or more combinations.
The method of arbitrary described lignocellulose ester catalysis process waste sulfuric acid from alkylation above, described auxiliary agent is catalyst for esterification reaction, and described catalyst for esterification reaction comprises AlCl
3,kNO
3, Na
2cO
3,li
2p
2o
7, Na
4p
2o
7,znCl
2, MgCO
3any or two or more combinations.
According to Changshu of those of ordinary skill in the art, described cellulosic solid waste is bagasse, cassava grain stillage, Cassava stalk, wood chip, bamboo bits, stalk, ramulus mori any or two or more combinations.Described drying is less than 15% for cellulosic solid waste is dried to water content, and described pulverizing is for be crushed to 20-60 order by cellulosic solid waste.
The method of above-described lignocellulose ester catalysis process waste sulfuric acid from alkylation, described oxygenant is the one in air, oxygen, hydrogen peroxide, ozone, clorox, Manganse Dioxide, sodium permanganate and dioxide peroxide.
The method of above-described lignocellulose ester catalysis process waste sulfuric acid from alkylation, the quality that described catalyzer and oxygenant add is respectively 0.2-5% and 1-20% of Waste Sulfuric Acid quality, and the quality that metal oxide adds is respectively the 25-95% of Waste Sulfuric Acid quality.
The method of above-described lignocellulose ester catalysis process waste sulfuric acid from alkylation, described redox reaction condition be temperature of reaction at 30-80 DEG C, reaction times 30-180min.
The method of arbitrary described lignocellulose ester catalysis process waste sulfuric acid from alkylation above, described slightly acidic pH value is 1.0-7.2.
The method of arbitrary described lignocellulose ester catalysis process waste sulfuric acid from alkylation above, the oxide compound of the element of metal and manganese, copper, zinc, aluminium element in the Ith and II race in the described metal oxide periodic table of elements.
The method of arbitrary described lignocellulose ester catalysis process waste sulfuric acid from alkylation above, described oxyhydroxide is the oxyhydroxide of the element of metal in the Ith and II race in the periodic table of elements.
Technique effect of the present invention and advantage:
(1) the lignocellulose ester surface selected by the present invention is containing a large amount of acid or basic group, particularly hydroxyl, phenolic hydroxyl group, carboxyl etc., there is the function of catalysis, active oxidation, energy catalytic oxidant produces living radical or the atomic oxygen of strong oxidizing property, make oxygenant activation, the degraded of accelerated reaction thing, meanwhile, catalyzer accelerates the transmission of Sauerstoffatom in system by effects such as complexings, enhances system oxygenizement equally.Lignocellulose ester selected by the present invention belongs to the heterogeneous catalyst of catalytic wet air oxidation process organic waste water, under its katalysis, the rapid reaction decomposes of oxygenant is made to go out active group (free radical), and then oxygenolysis organism, final product is CO
2, H
2o, N
2etc. harmless small-molecule substance.Waste residue after the method process, reaction solution all have no irritating odor, and reaction solution is as clear as crystal.Reaction solution can be used for producing inorganic salt after treatment, and the waste residue after handled may be used for producing fertilizer.
(2) the lignocellulose ester selected by the present invention also has adsorption bleaching function simultaneously, energy adsorption selection heavy metal and raising decolorizing effect, pH wide accommodation.
(3) the lignocellulose ester selected by the present invention not containing heavy metal, there will not be leaching ability of heavy metal with secondary pollution.
(4) the nontoxic and fully biodegradable of the lignocellulose ester selected by the present invention, the oxidative breakdown product of organic waste water is mainly water and carbonic acid gas and small molecules nontoxic on a small quantity.Simultaneously because raw material is solid waste and preparation technology simple, cost is low, and addition is few, and therefore catalyzer is not considered to reuse, and can act on bio-fertilizer raw material through solid-liquid separation after desorption heavy metal ion.
(5) the lignocellulose ester catalysis organic waste water oxidative degradation of application selected by the present invention can be carried out at ambient pressure, only needs the oxidative degradation device that band stirs, easy and simple to handle.Do not need to change original treatment process when being particularly applied in existing Waste Water Treatment, can directly apply.
Embodiment
The preparation of lignocellulose ester catalyst
Embodiment 1
The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1) raw materials pretreatment: bagasse fibre matter solid waste is dried to water content and is less than 15%, pulverizes be the cellulosic solid waste powder of 20 mesh sieves;
(2) high-speed mixing: by cellulosic solid waste powder, esterifying agent succsinic acid and auxiliary agent A lCl
3join mixing machine in the ratio of 100:5:1 to mix, obtain mixture;
(3) mechanical activation solid state reaction: said mixture grinding media heap volume is added in mechanical activation solid phase reactor according to the ratio of 100g:200ml, ball-milling reaction is carried out under rotating speed is 200rpm and 30 DEG C of water bath with thermostatic control temperature, after reaching 0.5h soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulose ester mixture;
(4) aftertreatment: lignocellulose ester mixture carries out granulation balling-up can obtain lignocellulose ester catalyst.
Embodiment 2
The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1) raw materials pretreatment: cassava grain stillage cellulosic solid waste is dried to water content and is less than 10%, pulverizes be the cellulosic solid waste powder of 25 mesh sieves;
(2) high-speed mixing: by cellulosic solid waste powder, esterifying agent toxilic acid and auxiliary agent KNO
3join mixing machine in the ratio of 100:10:2 to mix, obtain mixture;
(3) mechanical activation solid state reaction: said mixture grinding media heap volume is added in mechanical activation solid phase reactor according to the ratio of 100g:250ml, ball-milling reaction is carried out under rotating speed is 250rpm and 35 DEG C of water bath with thermostatic control temperature, after reaching 0.6h soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulose ester mixture;
(4) aftertreatment: lignocellulose ester mixture carries out granulation balling-up can obtain lignocellulose ester catalyst.
Embodiment 3
The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1) raw materials pretreatment: Cassava stalk cellulosic solid waste is dried to water content and is less than 5%, pulverizes be the cellulosic solid waste powder of 30 mesh sieves;
(2) high-speed mixing: by cellulosic solid waste powder, esterifying agent oxalic acid and auxiliary agent Na
2cO
3join mixing machine in the ratio of 100:15:3 to mix, obtain mixture;
(3) mechanical activation solid state reaction: said mixture grinding media heap volume is added in mechanical activation solid phase reactor according to the ratio of 100g:300ml, ball-milling reaction is carried out under rotating speed is 300rpm and 40 DEG C of water bath with thermostatic control temperature, after reaching 0.7h soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulose ester mixture;
(4) aftertreatment: lignocellulose ester mixture carries out granulation balling-up can obtain lignocellulose ester catalyst.
Embodiment 4
The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1) raw materials pretreatment: wood fiber matter solid waste is dried to water content and is less than 15%, pulverizes be the cellulosic solid waste powder of 35 mesh sieves;
(2) high-speed mixing: by cellulosic solid waste powder, esterifying agent citric acid and auxiliary agent Li
2p
2o
7join mixing machine in the ratio of 100:20:4 to mix, obtain mixture;
(3) mechanical activation solid state reaction: said mixture grinding media heap volume is added in mechanical activation solid phase reactor according to the ratio of 100g:350ml, ball-milling reaction is carried out under rotating speed is 350rpm and 45 DEG C of water bath with thermostatic control temperature, after reaching 0.8h soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulose ester mixture;
(4) aftertreatment: lignocellulose ester mixture carries out granulation balling-up can obtain lignocellulose ester catalyst.
Embodiment 5
The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1) raw materials pretreatment: bamboo is considered to be worth doing cellulosic solid waste and be dried to water content and be less than 5%, pulverize be the cellulosic solid waste powder of 40 mesh sieves;
(2) high-speed mixing: by cellulosic solid waste powder, esterifying agent butyric acid and auxiliary agent Na
4p
2o
7join mixing machine in the ratio of 100:25:5 to mix, obtain mixture;
(3) mechanical activation solid state reaction: said mixture grinding media heap volume is added in mechanical activation solid phase reactor according to the ratio of 100g:400ml, ball-milling reaction is carried out under rotating speed is 400rpm and 50 DEG C of water bath with thermostatic control temperature, after reaching 0.9h soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulose ester mixture;
(4) aftertreatment: lignocellulose ester mixture carries out granulation balling-up can obtain lignocellulose ester catalyst.
Embodiment 6
The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1) raw materials pretreatment: stalk fibre matter solid waste is dried to water content and is less than 8%, pulverizes be the cellulosic solid waste powder of 45 mesh sieves;
(2) high-speed mixing: by cellulosic solid waste powder, esterifying agent amino acid and auxiliary agent ZnCl
2join mixing machine in the ratio of 100:30:6 to mix, obtain mixture;
(3) mechanical activation solid state reaction: said mixture grinding media heap volume is added in mechanical activation solid phase reactor according to the ratio of 100g:450ml, ball-milling reaction is carried out under rotating speed is 450rpm and 55 DEG C of water bath with thermostatic control temperature, after reaching 1.0h soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulose ester mixture;
(4) aftertreatment: lignocellulose ester mixture carries out granulation balling-up can obtain lignocellulose ester catalyst.
Embodiment 7
The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1) raw materials pretreatment: ramulus mori cellulosic solid waste is dried to water content and is less than 15%, pulverizes be the cellulosic solid waste powder of 50 mesh sieves;
(2) high-speed mixing: by cellulosic solid waste powder, esterifying agent oxyacetic acid and auxiliary agent MgCO
3join mixing machine in the ratio of 100:35:7 to mix, obtain mixture;
(3) mechanical activation solid state reaction: said mixture grinding media heap volume is added in mechanical activation solid phase reactor according to the ratio of 100g:500ml, ball-milling reaction is carried out under rotating speed is 500rpm and 60 DEG C of water bath with thermostatic control temperature, after reaching 1.1h soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulose ester mixture;
(4) aftertreatment: lignocellulose ester mixture carries out granulation balling-up can obtain lignocellulose ester catalyst.
Embodiment 8
The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1) raw materials pretreatment: the cellulosic solid waste of bagasse, cassava grain stillage mixing is dried to water content and is less than 10%, pulverizes be the cellulosic solid waste powder of 60 mesh sieves;
(2) high-speed mixing: by cellulosic solid waste powder, esterifying agent n-caprylic acid and auxiliary agent A lCl
3join mixing machine in the ratio of 100:40:8 to mix, obtain mixture;
(3) mechanical activation solid state reaction: said mixture grinding media heap volume is added in mechanical activation solid phase reactor according to the ratio of 100g:550ml, ball-milling reaction is carried out under rotating speed is 550rpm and 38 DEG C of water bath with thermostatic control temperature, after reaching 1.2h soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulose ester mixture;
(4) aftertreatment: lignocellulose ester mixture carries out granulation balling-up can obtain lignocellulose ester catalyst.
Embodiment 9
The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1) raw materials pretreatment: the cellulosic solid waste of Cassava stalk, stalk, ramulus mori mixing is dried to water content and is less than 15%, pulverizes be the cellulosic solid waste powder of 40 mesh sieves;
(2) high-speed mixing: by cellulosic solid waste powder, esterifying agent (succsinic acid, toxilic acid mix in any proportion) and auxiliary agent (AlCl
3,kNO
3mix in any proportion) join mixing machine in the ratio of 100:20:2 and mix, obtain mixture;
(3) mechanical activation solid state reaction: said mixture grinding media heap volume is added in mechanical activation solid phase reactor according to the ratio of 100g:300ml, ball-milling reaction is carried out under rotating speed is 300rpm and 40 DEG C of water bath with thermostatic control temperature, after reaching 1.5h soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulose ester mixture;
(4) aftertreatment: lignocellulose ester mixture carries out granulation balling-up can obtain lignocellulose ester catalyst.
Embodiment 10
The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1) raw materials pretreatment: the cellulosic solid waste of Cassava stalk, stalk, ramulus mori mixing is dried to water content and is less than 15%, pulverizes be the cellulosic solid waste powder of 40 mesh sieves;
(2) high-speed mixing: by cellulosic solid waste powder, esterifying agent (oxalic acid, citric acid mix in any proportion) and auxiliary agent (Na
2cO
3,li
2p
2o
7mix in any proportion) join mixing machine in the ratio of 100:20:2 and mix, obtain mixture;
(3) mechanical activation solid state reaction: said mixture grinding media heap volume is added in mechanical activation solid phase reactor according to the ratio of 100g:300ml, ball-milling reaction is carried out under rotating speed is 300rpm and 40 DEG C of water bath with thermostatic control temperature, after reaching 1.5h soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulose ester mixture;
(4) aftertreatment: lignocellulose ester mixture carries out granulation balling-up can obtain lignocellulose ester catalyst.
Embodiment 11
The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1) raw materials pretreatment: the cellulosic solid waste of Cassava stalk, stalk, ramulus mori mixing is dried to water content and is less than 15%, pulverizes be the cellulosic solid waste powder of 40 mesh sieves;
(2) high-speed mixing: by cellulosic solid waste powder, esterifying agent (butyric acid, oxyacetic acid mix in any proportion) and auxiliary agent (ZnCl
2, MgCO
3mix in any proportion) join mixing machine in the ratio of 100:20:2 and mix, obtain mixture;
(3) mechanical activation solid state reaction: said mixture grinding media heap volume is added in mechanical activation solid phase reactor according to the ratio of 100g:300ml, ball-milling reaction is carried out under rotating speed is 300rpm and 40 DEG C of water bath with thermostatic control temperature, after reaching 1.5h soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulose ester mixture;
(4) aftertreatment: lignocellulose ester mixture carries out granulation balling-up can obtain lignocellulose ester catalyst.
Embodiment 12
The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1) raw materials pretreatment: the cellulosic solid waste of Cassava stalk, stalk, ramulus mori mixing is dried to water content and is less than 15%, pulverizes be the cellulosic solid waste powder of 40 mesh sieves;
(2) high-speed mixing: by cellulosic solid waste powder, esterifying agent (amino acid, n-caprylic acid, lauric acid mixes in any proportion) and auxiliary agent (AlCl
3,kNO
3, Na
2cO
3mix in any proportion) join mixing machine in the ratio of 100:20:2 and mix, obtain mixture;
(3) mechanical activation solid state reaction: said mixture grinding media heap volume is added in mechanical activation solid phase reactor according to the ratio of 100g:300ml, ball-milling reaction is carried out under rotating speed is 300rpm and 40 DEG C of water bath with thermostatic control temperature, after reaching 1.5h soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulose ester mixture;
(4) aftertreatment: lignocellulose ester mixture carries out granulation balling-up can obtain lignocellulose ester catalyst.
Embodiment 13
The preparation of lignocellulose ester catalyst, this preparation method comprises the following steps:
(1) raw materials pretreatment: the cellulosic solid waste of Cassava stalk, stalk, ramulus mori mixing is dried to water content and is less than 15%, pulverizes be the cellulosic solid waste powder of 40 mesh sieves;
(2) high-speed mixing: by cellulosic solid waste powder, esterifying agent (succsinic acid, toxilic acid, oxalic acid mix in any proportion) and auxiliary agent (Li
2p
2o
7, Na
4p
2o
7,znCl
2mix in any proportion) join mixing machine in the ratio of 100:20:2 and mix, obtain mixture;
(3) mechanical activation solid state reaction: said mixture grinding media heap volume is added in mechanical activation solid phase reactor according to the ratio of 100g:300ml, ball-milling reaction is carried out under rotating speed is 300rpm and 40 DEG C of water bath with thermostatic control temperature, after reaching 1.5h soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulose ester mixture;
(4) aftertreatment: lignocellulose ester mixture carries out granulation balling-up can obtain lignocellulose ester catalyst.
Embodiment 14
A kind of method of lignocellulose ester catalysis process waste sulfuric acid from alkylation, by mass concentration be 90.5% waste sulfuric acid from alkylation join in the IIth family metal oxide magnesium oxide of 42% of Waste Sulfuric Acid quality and react, be 7.2 for reaction end to its pH value, obtain mixed solution, mixed solution is filtered the reaction solution obtaining leached mud and black; Then in reaction solution, add the catalyzer lignocellulose ester prepared by embodiment 1 and oxygenant (hydrogen peroxide), the quality that catalyzer and oxygenant add is respectively 0.2% and 20% of Waste Sulfuric Acid quality, under 30 DEG C of conditions, redox reaction is there is in temperature of reaction, reaction times 30min, can be converted into CO completely by the organism in waste sulfuric acid from alkylation
2, H
2o, N
2etc. harmless small-molecule substance, solid-liquid separation, obtains cellulosic filter residue and as clear as crystal refined liquid.
Embodiment 15
A kind of method of lignocellulose ester catalysis process waste sulfuric acid from alkylation, the waste sulfuric acid from alkylation of 91% is joined in the IIth family metal oxide magnesium hydroxide of 55% of Waste Sulfuric Acid quality and react, be 6.9 for reaction end to its pH value, obtain mixed solution, mixed solution is filtered the reaction solution obtaining leached mud and black; Then in reaction solution, add the catalyzer lignocellulose ester prepared by embodiment 2 and oxygenant (air), the quality that catalyzer and oxygenant add is respectively 0.5% and 18% of Waste Sulfuric Acid quality, under 35 DEG C of conditions, redox reaction is there is in temperature of reaction, reaction times 50min, can be converted into CO completely by the organism in waste sulfuric acid from alkylation
2, H
2o, N
2etc. harmless small-molecule substance, solid-liquid separation, obtains cellulosic filter residue and as clear as crystal refined liquid.
Embodiment 16
A kind of method of lignocellulose ester catalysis process waste sulfuric acid from alkylation, the waste sulfuric acid from alkylation of 91.5% is joined in the IIth family metal oxide beryllium oxide of 20% of Waste Sulfuric Acid quality and react, be 2.0 for reaction end to its pH value, obtain mixed solution, mixed solution is filtered the reaction solution obtaining leached mud and black; Then in reaction solution, add the catalyzer lignocellulose ester prepared by embodiment 3 and oxygenant (oxygen), the quality that catalyzer and oxygenant add is respectively 1% and 16% of Waste Sulfuric Acid quality, under 40 DEG C of conditions, redox reaction is there is in temperature of reaction, reaction times 70min, can be converted into CO completely by the organism in waste sulfuric acid from alkylation
2, H
2o, N
2etc. harmless small-molecule substance, solid-liquid separation, obtains cellulosic filter residue and as clear as crystal refined liquid.
Embodiment 17
A kind of method of lignocellulose ester catalysis process waste sulfuric acid from alkylation, the waste sulfuric acid from alkylation of 92% is joined in the IIth race's oxyhydroxide beryllium hydroxide of 40% of Waste Sulfuric Acid quality and react, be 2.5 for reaction end to its pH value, obtain mixed solution, mixed solution is filtered the reaction solution obtaining leached mud and black; Then in reaction solution, add the catalyzer lignocellulose ester prepared by embodiment 4 and oxygenant (ozone), the quality that catalyzer and oxygenant add is respectively 1.5% and 14% of Waste Sulfuric Acid quality, under 45 DEG C of conditions, redox reaction is there is in temperature of reaction, reaction times 90min, can be converted into CO completely by the organism in waste sulfuric acid from alkylation
2, H
2o, N
2etc. harmless small-molecule substance, solid-liquid separation, obtains cellulosic filter residue and as clear as crystal refined liquid..
Embodiment 18
A kind of method of lignocellulose ester catalysis process waste sulfuric acid from alkylation, the waste sulfuric acid from alkylation of 92.5% is joined in the IIth family metal oxide calcium oxide of 55% of Waste Sulfuric Acid quality and react, be 6.4 for reaction end to its pH value, obtain mixed solution, mixed solution is filtered the reaction solution obtaining leached mud and black; Then in reaction solution, add the catalyzer lignocellulose ester prepared by embodiment 5 and oxygenant (hydrogen peroxide), the quality that catalyzer and oxygenant add is respectively 2% and 12% of Waste Sulfuric Acid quality, under 50 DEG C of conditions, redox reaction is there is in temperature of reaction, reaction times 110min, can be converted into CO completely by the organism in waste sulfuric acid from alkylation
2, H
2o, N
2etc. harmless small-molecule substance, solid-liquid separation, obtains cellulosic filter residue and as clear as crystal refined liquid.
Embodiment 19
A kind of method of lignocellulose ester catalysis process waste sulfuric acid from alkylation, the waste sulfuric acid from alkylation of 93% is joined in the IIth race's metal hydroxides calcium hydroxide of 60% of Waste Sulfuric Acid quality and react, be 6.5 for reaction end to its pH value, obtain mixed solution, mixed solution is filtered the reaction solution obtaining leached mud and black; Then in reaction solution, add the catalyzer lignocellulose ester prepared by embodiment 6 and oxygenant (air), the quality that catalyzer and oxygenant add is respectively 3% and 10% of Waste Sulfuric Acid quality, under 60 DEG C of conditions, redox reaction is there is in temperature of reaction, reaction times 130min, can be converted into CO completely by the organism in waste sulfuric acid from alkylation
2, H
2o, N
2etc. harmless small-molecule substance, solid-liquid separation, obtains cellulosic filter residue and as clear as crystal refined liquid.
Embodiment 20
A kind of method of lignocellulose ester catalysis process waste sulfuric acid from alkylation, the waste sulfuric acid from alkylation of 95% is joined in the IIth family metal oxide strontium oxide of 65% of Waste Sulfuric Acid quality and react, be 6.6 for reaction end to its pH value, obtain mixed solution, mixed solution is filtered the reaction solution obtaining leached mud and black; Then in reaction solution, add the catalyzer lignocellulose ester prepared by embodiment 7 and oxygenant (oxygen), the quality that catalyzer and oxygenant add is respectively 4% and 7% of Waste Sulfuric Acid quality, under 70 DEG C of conditions, redox reaction is there is in temperature of reaction, reaction times 150min, can be converted into CO completely by the organism in waste sulfuric acid from alkylation
2, H
2o, N
2etc. harmless small-molecule substance, solid-liquid separation, obtains cellulosic filter residue and as clear as crystal refined liquid.
Embodiment 21
A kind of method of lignocellulose ester catalysis process waste sulfuric acid from alkylation, the waste sulfuric acid from alkylation of 89% is joined in the IIth race's metal hydroxides strontium hydroxide of 70% of Waste Sulfuric Acid quality and react, be 6.7 for reaction end to its pH value, obtain mixed solution, mixed solution is filtered the reaction solution obtaining leached mud and black; Then in reaction solution, add the catalyzer lignocellulose ester prepared by embodiment 8 and oxygenant (ozone), the quality that catalyzer and oxygenant add is respectively 5% and 3% of Waste Sulfuric Acid quality, under 80 DEG C of conditions, redox reaction is there is in temperature of reaction, reaction times 170min, can be converted into CO completely by the organism in waste sulfuric acid from alkylation
2, H
2o, N
2etc. harmless small-molecule substance, solid-liquid separation, obtains cellulosic filter residue and as clear as crystal refined liquid.
Embodiment 22
A kind of method of lignocellulose ester catalysis process waste sulfuric acid from alkylation, the waste sulfuric acid from alkylation of 85% is joined in the Ith family metal oxide Lithium Oxide 98min of 25% of Waste Sulfuric Acid quality and react, be 3.0 for reaction end to its pH value, obtain mixed solution, mixed solution is filtered the reaction solution obtaining leached mud and black; Then in reaction solution, add the catalyzer lignocellulose ester prepared by embodiment 9 and oxygenant (ozone), the quality that catalyzer and oxygenant add is respectively 3.5% and 1% of Waste Sulfuric Acid quality, under 50 DEG C of conditions, redox reaction is there is in temperature of reaction, reaction times 180min, can be converted into CO completely by the organism in waste sulfuric acid from alkylation
2, H
2o, N
2etc. harmless small-molecule substance, solid-liquid separation, obtains cellulosic filter residue and as clear as crystal refined liquid.
Embodiment 23
A kind of method of lignocellulose ester catalysis process waste sulfuric acid from alkylation, the waste sulfuric acid from alkylation of 91% is joined in the Ith family metal oxide lithium hydroxide of 38% of Waste Sulfuric Acid quality and react, be 3.5 for reaction end to its pH value, obtain mixed solution, mixed solution is filtered the reaction solution obtaining leached mud and black; Then in reaction solution, add the catalyzer lignocellulose ester prepared by embodiment 2 and oxygenant (air), the quality that catalyzer and oxygenant add is respectively 0.5% and 18% of Waste Sulfuric Acid quality, under 35 DEG C of conditions, redox reaction is there is in temperature of reaction, reaction times 50min, can be converted into CO completely by the organism in waste sulfuric acid from alkylation
2, H
2o, N
2etc. harmless small-molecule substance, solid-liquid separation, obtains cellulosic filter residue and as clear as crystal refined liquid.
Embodiment 24
A kind of method of lignocellulose ester catalysis process waste sulfuric acid from alkylation, the waste sulfuric acid from alkylation of 91.5% is joined in the Ith family metal oxide sodium oxide of 58% of Waste Sulfuric Acid quality and react, be 7.0 for reaction end to its pH value, obtain mixed solution, mixed solution is filtered the reaction solution obtaining leached mud and black; Then in reaction solution, add the catalyzer lignocellulose ester prepared by embodiment 3 and oxygenant (oxygen), the quality that catalyzer and oxygenant add is respectively 1% and 16% of Waste Sulfuric Acid quality, under 40 DEG C of conditions, redox reaction is there is in temperature of reaction, reaction times 70min, can be converted into CO completely by the organism in waste sulfuric acid from alkylation
2, H
2o, N
2etc. harmless small-molecule substance, solid-liquid separation, obtains cellulosic filter residue and as clear as crystal refined liquid.
Embodiment 25
A kind of method of lignocellulose ester catalysis process waste sulfuric acid from alkylation, the waste sulfuric acid from alkylation of 92% is joined in the Ith race's oxyhydroxide sodium hydroxide of 37.5% of Waste Sulfuric Acid quality and react, be 7.1 for reaction end to its pH value, obtain mixed solution, mixed solution is filtered the reaction solution obtaining leached mud and black; Then in reaction solution, add the catalyzer lignocellulose ester prepared by embodiment 4 and oxygenant (ozone), the quality that catalyzer and oxygenant add is respectively 1.5% and 14% of Waste Sulfuric Acid quality, under 45 DEG C of conditions, redox reaction is there is in temperature of reaction, reaction times 90min, can be converted into CO completely by the organism in waste sulfuric acid from alkylation
2, H
2o, N
2etc. harmless small-molecule substance, solid-liquid separation, obtains cellulosic filter residue and as clear as crystal refined liquid.
Embodiment 26
A kind of method of lignocellulose ester catalysis process waste sulfuric acid from alkylation, the waste sulfuric acid from alkylation of 92.5% is joined in the Ith family metal oxide potassium oxide of 89% of Waste Sulfuric Acid quality and react, be 7.2 for reaction end to its pH value, obtain mixed solution, mixed solution is filtered the reaction solution obtaining leached mud and black; Then in reaction solution, add the catalyzer lignocellulose ester prepared by embodiment 5 and oxygenant (hydrogen peroxide), the quality that catalyzer and oxygenant add is respectively 2% and 12% of Waste Sulfuric Acid quality, under 50 DEG C of conditions, redox reaction is there is in temperature of reaction, reaction times 110min, can be converted into CO completely by the organism in waste sulfuric acid from alkylation
2, H
2o, N
2etc. harmless small-molecule substance, solid-liquid separation, obtains cellulosic filter residue and as clear as crystal refined liquid.
Embodiment 27
A kind of method of lignocellulose ester catalysis process waste sulfuric acid from alkylation, the waste sulfuric acid from alkylation of 93% is joined in the Ith race's metal hydroxides potassium hydroxide of 53% of Waste Sulfuric Acid quality and react, be 6.8 for reaction end to its pH value, obtain mixed solution, mixed solution is filtered the reaction solution obtaining leached mud and black; Then in reaction solution, add the catalyzer lignocellulose ester prepared by embodiment 6 and oxygenant (air), the quality that catalyzer and oxygenant add is respectively 3% and 10% of Waste Sulfuric Acid quality, under 60 DEG C of conditions, redox reaction is there is in temperature of reaction, reaction times 130min, can be converted into CO completely by the organism in waste sulfuric acid from alkylation
2, H
2o, N
2etc. harmless small-molecule substance, solid-liquid separation, obtains cellulosic filter residue and as clear as crystal refined liquid.
Embodiment 28
A kind of method of lignocellulose ester catalysis process waste sulfuric acid from alkylation, by mass concentration be 90.5% waste sulfuric acid from alkylation join in the metal oxide manganese of 65% of Waste Sulfuric Acid quality and react, be 5.0 for reaction end to its pH value, obtain mixed solution, mixed solution is filtered the reaction solution obtaining leached mud and black; Then in reaction solution, add the catalyzer lignocellulose ester prepared by embodiment 1 and oxygenant (hydrogen peroxide), the quality that catalyzer and oxygenant add is respectively 0.2% and 20% of Waste Sulfuric Acid quality, under 30 DEG C of conditions, redox reaction is there is in temperature of reaction, reaction times 30min, can be converted into CO completely by the organism in waste sulfuric acid from alkylation
2, H
2o, N
2etc. harmless small-molecule substance, solid-liquid separation, obtains cellulosic filter residue and as clear as crystal refined liquid.
Embodiment 29
A kind of method of lignocellulose ester catalysis process waste sulfuric acid from alkylation, the waste sulfuric acid from alkylation of 91.5% is joined in the metal oxide copper of 74% of Waste Sulfuric Acid quality and react, be 4.0 for reaction end to its pH value, obtain mixed solution, mixed solution is filtered the reaction solution obtaining leached mud and black; Then in reaction solution, add the catalyzer lignocellulose ester prepared by embodiment 3 and oxygenant (oxygen), the quality that catalyzer and oxygenant add is respectively 1% and 16% of Waste Sulfuric Acid quality, under 40 DEG C of conditions, redox reaction is there is in temperature of reaction, reaction times 70min, can be converted into CO completely by the organism in waste sulfuric acid from alkylation
2, H
2o, N
2etc. harmless small-molecule substance, solid-liquid separation, obtains cellulosic filter residue and as clear as crystal refined liquid.
Embodiment 30
A kind of method of lignocellulose ester catalysis process waste sulfuric acid from alkylation, the waste sulfuric acid from alkylation of 92.5% is joined in the metal oxide aluminium of 32% of Waste Sulfuric Acid quality and react, be 1.0 for reaction end to its pH value, obtain mixed solution, mixed solution is filtered the reaction solution obtaining leached mud and black; Then in reaction solution, add the catalyzer lignocellulose ester prepared by embodiment 5 and oxygenant (hydrogen peroxide), the quality that catalyzer and oxygenant add is respectively 2% and 12% of Waste Sulfuric Acid quality, under 50 DEG C of conditions, redox reaction is there is in temperature of reaction, reaction times 110min, can be converted into CO completely by the organism in waste sulfuric acid from alkylation
2, H
2o, N
2etc. harmless small-molecule substance, solid-liquid separation, obtains cellulosic filter residue and as clear as crystal refined liquid.
Claims (10)
1. the method for a lignocellulose ester catalysis process waste sulfuric acid from alkylation, it is characterized in that: waste sulfuric acid from alkylation is joined metal oxide or oxyhydroxide reaction, be slightly acidic to its pH value, then add catalyzer lignocellulose ester and oxygenant generation redox reaction, the organism in waste sulfuric acid from alkylation is converted into CO
2, H
2o, N
2harmless small-molecule substance.
2. the method for lignocellulose ester catalysis process waste sulfuric acid from alkylation according to claim 1, is characterized in that: described lignocellulose ester preparation method comprises the following steps:
(1) raw materials pretreatment: cellulosic solid waste is dry, pulverizing obtains cellulosic solid waste powder;
(2) high-speed mixing: join mixing machine in the ratio of cellulosic solid waste powder, esterifying agent and auxiliary agent 100:5-40:1-8 and mix, obtain mixture;
(3) mechanical activation solid state reaction: said mixture grinding media heap volume is added in mechanical activation solid phase reactor according to the ratio of 100g:200-600ml, ball-milling reaction is carried out under rotating speed is 200-600rpm and 30-60 DEG C of water bath with thermostatic control temperature, after reaching 0.5-1.5h soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulose ester mixture;
(4) aftertreatment: lignocellulose ester mixture carries out granulation balling-up can obtain lignocellulose ester catalyst.
3. the method for lignocellulose ester catalysis process waste sulfuric acid from alkylation according to claim 2, it is characterized in that: described esterifying agent is carboxylic acid, described carboxylic acid comprises succsinic acid, toxilic acid, oxalic acid, citric acid, butyric acid, oxyacetic acid, amino acid, n-caprylic acid, lauric acid any or two or more combinations.
4. the method for the lignocellulose ester catalysis process waste sulfuric acid from alkylation according to Claims 2 or 3, is characterized in that: described auxiliary agent is catalyst for esterification reaction, and described catalyst for esterification reaction comprises AlCl
3, KNO
3, Na
2cO
3, Li
2p
2o
7, Na
4p
2o
7, ZnCl
2, MgCO
3any or two or more combinations.
5. the method for lignocellulose ester catalysis process waste sulfuric acid from alkylation according to claim 1, is characterized in that: described oxygenant is the one in air, oxygen, hydrogen peroxide, ozone, clorox, Manganse Dioxide, sodium permanganate and dioxide peroxide.
6. the method for lignocellulose ester catalysis process waste sulfuric acid from alkylation according to claim 1, it is characterized in that: the quality that described catalyzer and oxygenant add is respectively 0.2-5% and 1-20% of Waste Sulfuric Acid quality, the quality that metal oxide or oxyhydroxide add for the theoretical amount required for the quality complete reaction at every turn processing Waste Sulfuric Acid.
7. the method for lignocellulose ester catalysis process waste sulfuric acid from alkylation according to claim 1, is characterized in that: described redox reaction condition be temperature of reaction at 30-80 DEG C, reaction times 30-180min.
8., according to the method for the arbitrary described lignocellulose ester catalysis process waste sulfuric acid from alkylation of claim 5-7, it is characterized in that: described slightly acidic pH value is 1.0-7.2.
9. the method for lignocellulose ester catalysis process waste sulfuric acid from alkylation according to claim 8, is characterized in that: described metal oxide is the oxide compound of the element of metal in the Ith and II race in the periodic table of elements and manganese, copper, zinc, aluminium element.
10. the method for lignocellulose ester catalysis process waste sulfuric acid from alkylation according to claim 8, is characterized in that: described oxyhydroxide is the oxyhydroxide of the element of metal in the Ith and II race in the periodic table of elements.
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