CN105565363B - A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares copper sulphate - Google Patents
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares copper sulphate Download PDFInfo
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Abstract
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares copper sulphate, waste sulfuric acid from alkylation is added in copper oxide or Kocide SD and is reacted, until its pH value is faintly acid, mixed liquor is obtained, mixed liquor is obtained by filtration leached mud and reaction solution；Then catalyst lignocellulosic ester is added in reaction solution and redox reaction occurs for oxidant, the organic matter in waste sulfuric acid from alkylation is fully converted to CO2、H2O、N2Etc. harmless small-molecule substance, separation of solid and liquid obtains cellulosic filter residue and refined liquid, and purity is can obtain after finally refined liquid is crystallized up to technical grade or the sulfuric acid copper products of feed grade.Lignocellulosic ester selected by the present invention not only has catalysis, but also has the function of active oxidation agent and adsorption bleaching；Production process does not introduce other impurity, will not cause secondary pollution, and the organic matter in spent acid obtains oxidative degradation, and mother liquor all recycles.
Description
Technical field
The invention belongs to treatment of Organic Wastewater field, specifically a kind of lignocellulosic ester should as oxidation catalyst
For the method for handling waste sulfuric acid from alkylation and preparing copper sulphate.
Background technology
With raising of the world to fuel demand, the widely used alkylation process production isooctane of oil plant, yield fly at present
Speed increases.It, need to be by the use of the sulfuric acid that concentration is 98% as urging when processing high-octane gasoline alkylate with alkyl plant
Agent often produces 1 ton of gasoline alkylate and just generates 80~100kg Waste Sulfuric Acids, 90% or so sulfuric acid contained in Waste Sulfuric Acid, 7% is left
Right organic matter and 3% or so water.Organic matter is mainly macromolecule alkene, alkadienes, alkyl sulfonic acid, sulfuric ester and vulcanization
Object etc., these material colors are deep, quality is sticky, Odor stimulation, it is difficult to thoroughly be removed from sulfuric acid.Existing maturation treatment technology
Mainly pyrolysis recycle is into sulfuric acid reuse, but equipment investment is huge, and it is huge to handle the costly of Waste Sulfuric Acid per ton, loss,
This brings great pressure to the cost and environment of manufacturing enterprise, is the biggest problem for perplexing enterprise's production.Other have extraction
Etc. treatment process, but extractant cost recovery is high, sulfuric acid content is low, there is not yet there is the enterprise of application.In addition, utilize alkyl
Changing Waste Sulfuric Acid production ammonium sulfate, magnesium sulfate, atlapulgite, precipitated silica, oil antirust agent etc. also has research, but due to cannot
Organic matter effectively in degradation removing Waste Sulfuric Acid, product have stronger penetrating odor, it is difficult to the product of high-purity is obtained, and
The inorganic agent of addition be easy to cause secondary pollution, and mother liquor is difficult to recycle.Therefore, waste sulfuric acid from alkylation still cannot at present
Effectively processing, largely overstocks in manufacturing enterprise, enterprise is made to face the risk of halt production, this will bring huge economic damage to enterprise
It loses.
Chinese patent title:A kind of method that magnesium sulfate and silico-calcium kieserite are produced using waste sulfuric acid from alkylation；Application is (specially
Profit) number:CN201410207898.X；The applying date:2014.05.18；Open (bulletin) number:CN104016385A；Open (bulletin)
Day:2014.09.03；A kind of method that magnesium sulfate and silico-calcium kieserite are produced using waste sulfuric acid from alkylation of the disclosure of the invention, is led to
Production magnesium sulfate consumption sulfuric acid is crossed, goes out acid-soluble oil waste residue using the suspended matters adsorbing separation such as silicon, calcium in miberal powder, using containing the dregs of fat
The heat of heat and waste active carbon auxiliary external heat source calcining waste residue, makes organic carbon, production mainly contains silicon-calcium-magnesium sulphur
Fertilizer.The beneficial effects of the invention are as follows：This method is simple for process, easy to operate, easy to implement, and equipment investment is few, cost
Low, non-secondary pollution, the byproduct silico-calcium kieserite market demand is big, economic and social benefit is notable, and the present invention makes all resources
It is obtained for optimization to use, is low cost, the ideal technology of processing alkylation spent acid.Principal claim:It is a kind of useless using alkylation
The method of gas washing in SA production magnesium sulfate and silico-calcium kieserite, it is characterised in that step is as follows：1) waste sulfuric acid from alkylation is preheating to 60-
100 DEG C, be added in the magnesite powder suspension of stirring and be reacted to basic bubble-free, add light burnt powder reacted to
Ph is 6.5-7.2, obtains mixed liquor；2) by the isolated mother liquor of above-mentioned mixed liquor press filtration and a waste residue, once female
After oxidant and activated carbon are added in liquid and stirs decoloration, press filtration again obtains refinement mother liquor and activated carbon waste residue, refinement mother liquor
By crystallizing, centrifuging, drying, epsom salt is made；3) waste residue and activated carbon waste residue are uniformly mixed, in 700-1100
It after being calcined at DEG C, is granulated with magnesium sulfate powder, you can silico-calcium kieserite is made.But the oxidant that this method is selected compares
Costliness, process costs are higher；This method selects activated carbon to decolourize, the easy adsorption saturation of activated carbon, and decoloration is often not thorough,
Therefore this method cannot it is fully effective degradation removing Waste Sulfuric Acid in organic matter.
The content of the invention
In view of the above problems, the present invention develops a kind of lignocellulosic ester catalysis processing waste sulfuric acid from alkylation system
The method of standby copper sulphate, this method treated waste residue, refined liquid have no irritating odor, and refined liquid is as clear as crystal, refined liquid
The copper sulphate of high-purity is obtained after crystallized, is obtained as organic compost is carried out after leached mud and cellulosic the filter residue mixing of discarded object
To degradable organic fertilizer base-material.
The specific technical solution of the present invention is as follows：
The method that a kind of lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares copper sulphate, by waste sulfuric acid from alkylation plus
Enter into copper oxide or Kocide SD and react, until its pH value is faintly acid, obtains mixed liquor, leached mud is obtained by filtration in mixed liquor
And reaction solution；Then catalyst lignocellulosic ester is added in reaction solution and redox reaction occurs for oxidant, by alkyl
It is CO to change the organic matter in Waste Sulfuric Acid by deep oxidation Degradation and Transformation2、H2O、N2Etc. harmless small-molecule substance, separation of solid and liquid obtains
To cellulosic filter residue and refined liquid, purity is can obtain after finally refined liquid is crystallized up to technical grade or the copper sulphate of feed grade
Product.
The method that above-described lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares copper sulphate, described is wooden
Cellulose esters preparation method comprises the following steps：
(1) pretreatment of raw material：The drying of cellulosic solid waste, crushing are obtained into cellulosic solid waste powder；
(2) mixed at high speed：By cellulosic solid waste powder, esterifying agent and auxiliary agent 100：5-40：The ratio of 1-8 is added to mixed
Conjunction machine is uniformly mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:The ratio of 200-600ml
It adds in mechanical activation solid phase reactor, it is anti-to carry out ball milling at a temperature of rotating speed is 200-600rpm and 30-60 DEG C of water bath with thermostatic control
Should, after reaching 0.5-1.5h soak times, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain wooden fibre
The plain ester admixture of dimension；
(4) post-process：Lignocellulosic ester admixture, which carries out granulation balling-up, can obtain lignocellulosic ester catalyst.
The method that above-described lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares copper sulphate, the esterification
Agent is carboxylic acid, and the carboxylic acid includes succinic acid, maleic acid, oxalic acid, citric acid, butyric acid, glycolic, amino acid, just pungent
Acid, any or two or more combination of lauric acid.
The method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation described in any of the above prepares copper sulphate, it is described
Auxiliary agent is catalyst for esterification reaction, the catalyst for esterification reaction mantoquita, and the mantoquita is copper nitrate, copper sulphate, carbonic acid
One or two kinds of object mixed above in copper.
According to Changshu of those of ordinary skill in the art, the cellulosic solid waste is bagasse, cassava grain stillage, cassava
Any or two or more combination of bar, sawdust, bamboo scraps, stalk, ramulus mori.
The drying is that cellulosic solid waste is dried to water content less than 15%, and the crushing is to consolidate cellulosic
Waste was crushed to 20-60 mesh sieves.
The method that above-described lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares copper sulphate, the oxidation
Agent is one kind in air, oxygen, hydrogen peroxide and ozone
The method that above-described lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares copper sulphate, the catalysis
The quality that agent and oxidant add in is respectively the 0.2-5% and 1-20% of Waste Sulfuric Acid quality, what copper oxide or Kocide SD added in
Quality is the 68-95% of Waste Sulfuric Acid quality.
The method that above-described lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares copper sulphate, the oxidation is also
Former reaction condition is reaction temperature at 30-80 DEG C, reaction time 30-180min.
The method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation described in any of the above prepares copper sulphate, it is described
Faintly acid pH value is 2.0-4.0.
The method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation described in any of the above prepares copper sulphate, feature
It is：Organic compost, which is carried out, after the leached mud and the mixing of cellulosic filter residue obtains degradable organic fertilizer base-material.
The technique effect and advantage of the present invention：
(1) a large amount of acid or basic groups, particularly hydroxyl, phenol are contained in the lignocellulosic ester surface selected by the present invention
Hydroxyl, carboxyl etc., have the function of catalysis, active oxidation, and energy catalytic oxidant generates the living radical or original of strong oxidizing property
Sub- oxygen makes oxidant activation, accelerates reactant degradation, meanwhile, the effects that catalyst passes through complexing, accelerates oxygen atom in system
Transmission, equally enhance system oxidation.This method treated cellulosic filter residue and refined liquid have no irritating odor,
Refined liquid is as clear as crystal.Existing technology cannot it is fully effective degradation removing Waste Sulfuric Acid in organic matter, still have stronger stimulation
Property smell and deeper color.
(2) the lignocellulosic ester selected by the present invention belongs to catalytic wet air oxidation processing the heterogeneous of organic wastewater and urges
Agent under its catalytic action, makes oxidant react rapidly and decomposites active group (free radical), and then oxygenolysis is organic
Object, final product CO2、H2O and N2Innocuous substances are waited, separation of solid and liquid obtains cellulosic filter residue and refined liquid, finally will be refined
Technical grade or the sulfuric acid copper products of feed grade are can obtain after liquid crystallization.Though the and purity for the copper sulphate that the prior art is prepared
Technical grade can so be reached, but feed grade is not achieved, while appearance is poor, and have penetrating odor.
(3) the lignocellulosic ester selected by the present invention is not in the secondary of heavy metal dissolution institute band without heavy metal
Pollution.
(4) selected by the present invention lignocellulosic ester is nontoxic and fully biodegradable, the oxidative degradation of organic wastewater
Product is mainly water and carbon dioxide and a small amount of nontoxic small molecule.
(5) the lignocellulosic ester selected by the present invention just selects catalyst of the mantoquita as esterification in the preparation,
Effectively reduce the introducing of other chemical impurities so that the purity of finally prepd copper sulphate is able to larger raising.
(6) raw material that the lignocellulosic ester selected by the present invention is selected in the preparation is solid waste and preparation process letter
Single, at low cost, additive amount is few, therefore catalyst can be made without considering reuse after through separation of solid and liquid and being desorbed heavy metal ion
With bio-fertilizer raw material.
(7) can be carried out under normal pressure using the lignocellulosic ester catalysis organic wastewater oxidative degradation selected by the present invention,
The oxidative degradation device with stirring is only needed, it is easy to operate.It particularly applies and is varied without when having waste water treatment system
Originally treatment process can be applied directly.
Specific embodiment
The preparation of lignocellulosic ester catalyst
Embodiment 1
The preparation of lignocellulosic ester catalyst, the preparation method comprise the following steps：
(1) pretreatment of raw material：Bagasse fibre matter solid waste drying to water content is less than 15%, crushing and obtained 20 mesh
The cellulosic solid waste powder of sieve；
(2) mixed at high speed：Cellulosic solid waste powder, esterifying agent succinic acid and auxiliary agent (for copper nitrate) are pressed 100：5：1
Ratio be added to mixer and be uniformly mixed, obtain mixture；
(3) mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:The ratio of 200ml adds in
In mechanical activation solid phase reactor, ball-milling reaction is carried out at a temperature of rotating speed is 200rpm and 30 DEG C of water bath with thermostatic control, reaches 0.5h
After soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulosic ester admixture；
(4) post-process：Lignocellulosic ester admixture, which carries out granulation balling-up, can obtain lignocellulosic ester catalyst.
Embodiment 2
The preparation of lignocellulosic ester catalyst, the preparation method comprise the following steps：
(1) pretreatment of raw material：Cassava grain stillage cellulosic solid waste drying to water content is less than 10%, crushing and obtained 25
The cellulosic solid waste powder of mesh sieve；
(2) mixed at high speed：Cellulosic solid waste powder, esterifying agent maleic acid and auxiliary agent (for copper sulphate) are pressed 100：10：2
Ratio be added to mixer and be uniformly mixed, obtain mixture；
(3) mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:The ratio of 250ml adds in
In mechanical activation solid phase reactor, ball-milling reaction is carried out at a temperature of rotating speed is 250rpm and 35 DEG C of water bath with thermostatic control, reaches 0.6h
After soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulosic ester admixture；
(4) post-process：Lignocellulosic ester admixture, which carries out granulation balling-up, can obtain lignocellulosic ester catalyst.
Embodiment 3
The preparation of lignocellulosic ester catalyst, the preparation method comprise the following steps：
(1) pretreatment of raw material：Cassava stalk cellulosic solid waste drying to water content is less than 5%, crushing and obtained 30 mesh
The cellulosic solid waste powder of sieve；
(2) mixed at high speed：Cellulosic solid waste powder, esterifying agent oxalic acid and auxiliary agent (for copper carbonate) are pressed 100：15：3
Ratio is added to mixer and is uniformly mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:The ratio of 300ml adds in
In mechanical activation solid phase reactor, ball-milling reaction is carried out at a temperature of rotating speed is 300rpm and 40 DEG C of water bath with thermostatic control, reaches 0.7h
After soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulosic ester admixture；
(4) post-process：Lignocellulosic ester admixture, which carries out granulation balling-up, can obtain lignocellulosic ester catalyst.
Embodiment 4
The preparation of lignocellulosic ester catalyst, the preparation method comprise the following steps：
(1) pretreatment of raw material：Wood fiber matter solid waste drying to water content is less than 15%, crushing and obtained 35 mesh sieves
Cellulosic solid waste powder；
(2) mixed at high speed：By cellulosic solid waste powder, esterifying agent citric acid and auxiliary agent (for two kinds of copper nitrate, copper sulphate
The mixture mixed in any proportion) by 100：20：4 ratio is added to mixer and is uniformly mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:The ratio of 350ml adds in
In mechanical activation solid phase reactor, ball-milling reaction is carried out at a temperature of rotating speed is 350rpm and 45 DEG C of water bath with thermostatic control, reaches 0.8h
After soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulosic ester admixture；
(4) post-process：Lignocellulosic ester admixture, which carries out granulation balling-up, can obtain lignocellulosic ester catalyst.
Embodiment 5
The preparation of lignocellulosic ester catalyst, the preparation method comprise the following steps：
(1) pretreatment of raw material：Bamboo scraps cellulosic solid waste drying to water content is less than 5%, crushing and obtained 40 mesh sieves
Cellulosic solid waste powder；
(2) mixed at high speed：Cellulosic solid waste powder, esterifying agent butyric acid and auxiliary agent (are pressed for copper nitrate, two kinds of copper carbonate
The mixture of arbitrary proportion mixing) press 100：25：5 ratio is added to mixer and is uniformly mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:The ratio of 400ml adds in
In mechanical activation solid phase reactor, ball-milling reaction is carried out at a temperature of rotating speed is 400rpm and 50 DEG C of water bath with thermostatic control, reaches 0.9h
After soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulosic ester admixture；
(4) post-process：Lignocellulosic ester admixture, which carries out granulation balling-up, can obtain lignocellulosic ester catalyst.
Embodiment 6
The preparation of lignocellulosic ester catalyst, the preparation method comprise the following steps：
(1) pretreatment of raw material：Stalk fibre matter solid waste drying to water content is less than 8%, crushing and obtained 45 mesh sieves
Cellulosic solid waste powder；
(2) mixed at high speed：By cellulosic solid waste powder, esterifying agent amino acid and auxiliary agent (for two kinds of copper sulphate, copper carbonate
The mixture mixed in any proportion) by 100：30：6 ratio is added to mixer and is uniformly mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:The ratio of 450ml adds in
In mechanical activation solid phase reactor, ball-milling reaction is carried out at a temperature of rotating speed is 450rpm and 55 DEG C of water bath with thermostatic control, reaches 1.0h
After soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulosic ester admixture；
(4) post-process：Lignocellulosic ester admixture, which carries out granulation balling-up, can obtain lignocellulosic ester catalyst.
Embodiment 7
The preparation of lignocellulosic ester catalyst, the preparation method comprise the following steps：
(1) pretreatment of raw material：Ramulus mori cellulosic solid waste drying to water content is less than 15%, crushing and obtained 50 mesh sieves
Cellulosic solid waste powder；
(2) mixed at high speed：Cellulosic solid waste powder, esterifying agent glycolic and auxiliary agent (for copper nitrate) are pressed 100：35：7
Ratio be added to mixer and be uniformly mixed, obtain mixture；
(3) mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:The ratio of 500ml adds in
In mechanical activation solid phase reactor, ball-milling reaction is carried out at a temperature of rotating speed is 500rpm and 60 DEG C of water bath with thermostatic control, reaches 1.1h
After soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulosic ester admixture；
(4) post-process：Lignocellulosic ester admixture, which carries out granulation balling-up, can obtain lignocellulosic ester catalyst.
Embodiment 8
The preparation of lignocellulosic ester catalyst, the preparation method comprise the following steps：
(1) pretreatment of raw material：Cellulosic solid waste drying to the water content that bagasse, cassava grain stillage mix is less than
10%th, crush and obtained the cellulosic solid waste powder of 60 mesh sieves；
(2) mixed at high speed：Cellulosic solid waste powder, esterifying agent caprylic acid and auxiliary agent (for copper sulphate) are pressed 100：40：8
Ratio be added to mixer and be uniformly mixed, obtain mixture；
(3) mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:The ratio of 550ml adds in
In mechanical activation solid phase reactor, ball-milling reaction is carried out at a temperature of rotating speed is 550rpm and 38 DEG C of water bath with thermostatic control, reaches 1.2h
After soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulosic ester admixture；
(4) post-process：Lignocellulosic ester admixture, which carries out granulation balling-up, can obtain lignocellulosic ester catalyst.
Embodiment 9
The preparation of lignocellulosic ester catalyst, the preparation method comprise the following steps：
(1) pretreatment of raw material：Cellulosic solid waste drying to the water content that Cassava stalk, stalk, ramulus mori mix is less than
15%th, crush and obtained the cellulosic solid waste powder of 60 mesh sieves；
(2) mixed at high speed：Cellulosic solid waste powder, esterifying agent lauric acid and auxiliary agent (for copper carbonate) are pressed 100：20：2
Ratio be added to mixer and be uniformly mixed, obtain mixture；
(3) mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:The ratio of 300ml adds in
In mechanical activation solid phase reactor, ball-milling reaction is carried out at a temperature of rotating speed is 300rpm and 40 DEG C of water bath with thermostatic control, reaches 1.5h
After soak time, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulosic ester admixture；
(4) post-process：Lignocellulosic ester admixture, which carries out granulation balling-up, can obtain lignocellulosic ester catalyst.
Embodiment 10
A kind of lignocellulosic ester catalysis handles the method that waste sulfuric acid from alkylation prepares copper sulphate, is by mass concentration
90.5% waste sulfuric acid from alkylation, which is added in 72% copper oxide of Waste Sulfuric Acid quality, to react, until it 2.0 is reaction that its pH value, which is,
Terminal obtains mixed liquor, and mixed liquor is obtained by filtration to the reaction solution of leached mud and black；Then embodiment is added in reaction solution
The quality that catalyst lignocellulosic ester and oxidant (hydrogen peroxide) prepared by 1, catalyst and oxidant add in is respectively useless
The 0.2% of sulfuric acid quality and 20%, occur redox reaction under the conditions of 30 DEG C in reaction temperature, reaction time 30min, i.e.,
Organic matter in waste sulfuric acid from alkylation can be fully converted to CO2、H2O、N2Etc. harmless small-molecule substance, separation of solid and liquid obtains fibre
Tie up matter filter residue and as clear as crystal refined liquid, finally refined liquid is crystallized, is centrifuged, dry after can obtain purity up to work
The sulfuric acid copper products of industry grade or feed grade, product is pure white, has no irritating odor.Had after leached mud and the mixing of cellulosic filter residue
Machine compost obtains degradable organic fertilizer base-material.
Embodiment 11
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares copper sulphate, 91% alkylation is given up
Sulfuric acid, which is added in 90% Kocide SD of Waste Sulfuric Acid quality, to react, until it 2.2 is reaction end that its pH value, which is, is mixed
The reaction solution of leached mud and black is obtained by filtration in mixed liquor by liquid；Then the catalysis prepared by embodiment 2 is added in reaction solution
The quality that agent lignocellulosic ester and oxidant (air), catalyst and oxidant add in is respectively the 0.5% of Waste Sulfuric Acid quality
With 18%, redox reaction, reaction time 50min occur under the conditions of 35 DEG C in reaction temperature, you can sulfur waste will be alkylated
Organic matter in acid is fully converted to CO2、H2O、N2Etc. harmless small-molecule substance, separation of solid and liquid obtains cellulosic filter residue and limpid
Transparent refined liquid, finally refined liquid is crystallized, is centrifuged, dry after can obtain purity up to technical grade or feed grade
Sulfuric acid copper products, product is pure white, has no irritating odor.Organic compost is carried out after leached mud and the mixing of cellulosic filter residue to obtain to drop
The organic fertilizer base-material of solution.
Embodiment 12
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares copper sulphate, by 91.5% alkylation
Waste Sulfuric Acid, which is added in 73% copper oxide of Waste Sulfuric Acid quality, to react, until it 2.4 is reaction end that its pH value, which is, is mixed
The reaction solution of leached mud and black is obtained by filtration in mixed liquor by liquid；Then the catalysis prepared by embodiment 3 is added in reaction solution
The quality that agent lignocellulosic ester and oxidant (oxygen), catalyst and oxidant add in is respectively 1% He of Waste Sulfuric Acid quality
16%, redox reaction, reaction time 70min occur under the conditions of 40 DEG C in reaction temperature, you can by waste sulfuric acid from alkylation
In organic matter be fully converted to CO2、H2O、N2Etc. harmless small-molecule substance, separation of solid and liquid obtains cellulosic filter residue and limpid
Bright refined liquid, finally refined liquid is crystallized, is centrifuged, dry after can obtain purity up to technical grade or the sulphur of feed grade
Sour copper products, product is pure white, has no irritating odor.Progress organic compost obtains degradable after leached mud and the mixing of cellulosic filter residue
Organic fertilizer base-material.
Embodiment 13
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares copper sulphate, 92% alkylation is given up
Sulfuric acid, which is added in 91% Kocide SD of Waste Sulfuric Acid quality, to react, until it 2.6 is reaction end that its pH value, which is, is mixed
The reaction solution of leached mud and black is obtained by filtration in mixed liquor by liquid；Then the catalysis prepared by embodiment 4 is added in reaction solution
The quality that agent lignocellulosic ester and oxidant (ozone), catalyst and oxidant add in is respectively the 1.5% of Waste Sulfuric Acid quality
With 14%, redox reaction, reaction time 90min occur under the conditions of 45 DEG C in reaction temperature, you can sulfur waste will be alkylated
Organic matter in acid is fully converted to CO2、H2O、N2Etc. harmless small-molecule substance, separation of solid and liquid obtains cellulosic filter residue and limpid
Transparent refined liquid, finally refined liquid is crystallized, is centrifuged, dry after can obtain purity up to technical grade or feed grade
Sulfuric acid copper products, product is pure white, has no irritating odor.Organic compost is carried out after leached mud and the mixing of cellulosic filter residue to obtain to drop
The organic fertilizer base-material of solution.
Embodiment 14
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares copper sulphate, by 92.5% alkylation
Waste Sulfuric Acid, which is added in 75% copper oxide of Waste Sulfuric Acid quality, to react, until it 2.8 is reaction end that its pH value, which is, is mixed
The reaction solution of leached mud and black is obtained by filtration in mixed liquor by liquid；Then the catalysis prepared by embodiment 5 is added in reaction solution
The quality that agent lignocellulosic ester and oxidant (hydrogen peroxide), catalyst and oxidant add in is respectively the 2% of Waste Sulfuric Acid quality
With 12%, redox reaction, reaction time 110min occur under the conditions of 50 DEG C in reaction temperature, you can sulfur waste will be alkylated
Organic matter in acid is fully converted to CO2、H2O、N2Etc. harmless small-molecule substance, separation of solid and liquid obtains cellulosic filter residue and limpid
Transparent refined liquid, finally refined liquid is crystallized, is centrifuged, dry after can obtain purity up to technical grade or feed grade
Sulfuric acid copper products, product is pure white, has no irritating odor.Organic compost is carried out after leached mud and the mixing of cellulosic filter residue to obtain to drop
The organic fertilizer base-material of solution.
Embodiment 15
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares copper sulphate, 93% alkylation is given up
Sulfuric acid, which is added in 92% Kocide SD of Waste Sulfuric Acid quality, to react, until it 3.0 is reaction end that its pH value, which is, is mixed
The reaction solution of leached mud and black is obtained by filtration in mixed liquor by liquid；Then the catalysis prepared by embodiment 6 is added in reaction solution
The quality that agent lignocellulosic ester and oxidant (air), catalyst and oxidant add in is respectively 3% He of Waste Sulfuric Acid quality
10%, redox reaction, reaction time 130min occur under the conditions of 60 DEG C in reaction temperature, you can by waste sulfuric acid from alkylation
In organic matter be fully converted to CO2、H2O、N2Etc. harmless small-molecule substance, separation of solid and liquid obtains cellulosic filter residue and limpid
Bright refined liquid, finally refined liquid is crystallized, is centrifuged, dry after can obtain purity up to technical grade or the sulphur of feed grade
Sour copper products, product is pure white, has no irritating odor.Progress organic compost obtains degradable after leached mud and the mixing of cellulosic filter residue
Organic fertilizer base-material.
Embodiment 16
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares copper sulphate, 95% alkylation is given up
Sulfuric acid, which is added in 95% Kocide SD of Waste Sulfuric Acid quality, to react, until it 3.2 is reaction end that its pH value, which is, is mixed
The reaction solution of leached mud and black is obtained by filtration in mixed liquor by liquid；Then the catalysis prepared by embodiment 7 is added in reaction solution
The quality that agent lignocellulosic ester and oxidant (oxygen), catalyst and oxidant add in is respectively 4% He of Waste Sulfuric Acid quality
7%, redox reaction, reaction time 150min occur under the conditions of 70 DEG C in reaction temperature, you can by waste sulfuric acid from alkylation
In organic matter be fully converted to CO2、H2O、N2Etc. harmless small-molecule substance, separation of solid and liquid obtains cellulosic filter residue and limpid
Bright refined liquid, finally refined liquid is crystallized, is centrifuged, dry after can obtain purity up to technical grade or the sulphur of feed grade
Sour copper products, product is pure white, has no irritating odor.Progress organic compost obtains degradable after leached mud and the mixing of cellulosic filter residue
Organic fertilizer base-material.
Embodiment 17
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares copper sulphate, 89% alkylation is given up
Sulfuric acid, which is added in 72% copper oxide of Waste Sulfuric Acid quality, to react, until it 3.4 is reaction end that its pH value, which is, obtains mixed liquor,
Mixed liquor is obtained by filtration to the reaction solution of leached mud and black；Then the catalyst prepared by embodiment 8 is added in reaction solution
The quality that lignocellulosic ester and oxidant (ozone), catalyst and oxidant add in is respectively 5% He of Waste Sulfuric Acid quality
3%, redox reaction, reaction time 170min occur under the conditions of 80 DEG C in reaction temperature, you can by waste sulfuric acid from alkylation
In organic matter be fully converted to CO2、H2O、N2Etc. harmless small-molecule substance, separation of solid and liquid obtains cellulosic filter residue and limpid
Bright refined liquid, finally refined liquid is crystallized, is centrifuged, dry after can obtain purity up to technical grade or the sulphur of feed grade
Sour copper products, product is pure white, has no irritating odor.Progress organic compost obtains degradable after leached mud and the mixing of cellulosic filter residue
Organic fertilizer base-material.
Embodiment 18
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares copper sulphate, 85% alkylation is given up
Sulfuric acid, which is added in 68% copper oxide of Waste Sulfuric Acid quality, to react, until it 3.6 is reaction end that its pH value, which is, obtains mixed liquor,
Mixed liquor is obtained by filtration to the reaction solution of leached mud and black；Then the catalyst prepared by embodiment 9 is added in reaction solution
The quality that lignocellulosic ester and oxidant (ozone), catalyst and oxidant add in is respectively 3.5% He of Waste Sulfuric Acid quality
1%, redox reaction, reaction time 180min occur under the conditions of 50 DEG C in reaction temperature, you can by waste sulfuric acid from alkylation
In organic matter be fully converted to CO2、H2O、N2Etc. harmless small-molecule substance, separation of solid and liquid obtains cellulosic filter residue and limpid
Bright refined liquid, finally refined liquid is crystallized, is centrifuged, dry after can obtain purity up to technical grade or the sulphur of feed grade
Sour copper products, product is pure white, has no irritating odor.Progress organic compost obtains degradable after leached mud and the mixing of cellulosic filter residue
Organic fertilizer base-material.
Embodiment 19
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares copper sulphate, 89% alkylation is given up
Sulfuric acid, which is added in 88% Kocide SD of Waste Sulfuric Acid quality, to react, until it 3.8 is reaction end that its pH value, which is, is mixed
The reaction solution of leached mud and black is obtained by filtration in mixed liquor by liquid；Then the catalysis prepared by embodiment 8 is added in reaction solution
The quality that agent lignocellulosic ester and oxidant (ozone), catalyst and oxidant add in is respectively 5% He of Waste Sulfuric Acid quality
3%, redox reaction, reaction time 170min occur under the conditions of 80 DEG C in reaction temperature, you can by waste sulfuric acid from alkylation
In organic matter be fully converted to CO2、H2O、N2Etc. harmless small-molecule substance, separation of solid and liquid obtains cellulosic filter residue and limpid
Bright refined liquid, finally refined liquid is crystallized, is centrifuged, dry after can obtain purity up to technical grade or the sulphur of feed grade
Sour copper products, product is pure white, has no irritating odor.Progress organic compost obtains degradable after leached mud and the mixing of cellulosic filter residue
Organic fertilizer base-material.
Embodiment 20
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares copper sulphate, 87% alkylation is given up
Sulfuric acid, which is added in 70% copper oxide of Waste Sulfuric Acid quality, to react, until it 4.0 is reaction end that its pH value, which is, obtains mixed liquor,
Mixed liquor is obtained by filtration to the reaction solution of leached mud and black；Then the catalyst prepared by embodiment 9 is added in reaction solution
The quality that lignocellulosic ester and oxidant (ozone), catalyst and oxidant add in is respectively 3.5% He of Waste Sulfuric Acid quality
1%, redox reaction, reaction time 180min occur under the conditions of 50 DEG C in reaction temperature, you can by waste sulfuric acid from alkylation
In organic matter be fully converted to CO2、H2O、N2Etc. harmless small-molecule substance, separation of solid and liquid obtains cellulosic filter residue and limpid
Bright refined liquid, finally refined liquid is crystallized, is centrifuged, dry after can obtain purity up to technical grade or the sulphur of feed grade
Sour copper products, product is pure white, has no irritating odor.Progress organic compost obtains degradable after leached mud and the mixing of cellulosic filter residue
Organic fertilizer base-material.
Claims (8)
1. a kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares copper sulphate, it is characterised in that：By alkyl
Change Waste Sulfuric Acid, which is added in copper oxide or Kocide SD, to react, until its pH value is faintly acid, obtains mixed liquor, mixed liquor is filtered
Obtain leached mud and reaction solution；Then catalyst lignocellulosic ester is added in reaction solution and oxidant generation redox is anti-
Should, the organic matter in waste sulfuric acid from alkylation is fully converted to CO2、H2O、N2Harmless small-molecule substance, separation of solid and liquid obtain fibre
Matter filter residue and refined liquid are tieed up, purity is can obtain after finally refined liquid is crystallized and is produced up to technical grade or the copper sulphate of feed grade
Product;The lignocellulosic ester preparation method comprises the following steps：
（1）Pretreatment of raw material：The drying of cellulosic solid waste, crushing are obtained into cellulosic solid waste powder；
（2）Mixed at high speed：By cellulosic solid waste powder, esterifying agent and auxiliary agent 100：5-40：The ratio of 1-8 is added to mixer
It is uniformly mixed, obtains mixture；
（3）Mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:The ratio of 200-600mL adds in
In mechanical activation solid phase reactor, ball-milling reaction is carried out at a temperature of rotating speed is 200-600rpm and 30-60 DEG C of water bath with thermostatic control, is reached
To after 0.5-1.5h soak times, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain lignocellulosic
Ester admixture；
（4）Post processing：Lignocellulosic ester admixture, which carries out granulation balling-up, can obtain lignocellulosic ester catalyst.
2. the method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation according to claim 1 prepares copper sulphate,
It is characterized in that：The esterifying agent be carboxylic acid, the carboxylic acid include succinic acid, maleic acid, oxalic acid, citric acid, butyric acid,
Glycolic, amino acid, caprylic acid, any or two or more combination of lauric acid.
3. the method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation according to claim 1 or 2 prepares copper sulphate,
It is characterized in that：The auxiliary agent is catalyst for esterification reaction, and the catalyst for esterification reaction is mantoquita, and the mantoquita is
One or two kinds of object mixed above in copper nitrate, copper sulphate, copper carbonate.
4. the method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation according to claim 1 prepares copper sulphate,
It is characterized in that：The oxidant is one kind in air, oxygen, hydrogen peroxide and ozone.
5. the method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation according to claim 1 prepares copper sulphate,
It is characterized in that：The quality that the catalyst and oxidant add in is respectively the 0.2-5% and 1-20% of Waste Sulfuric Acid quality, copper oxide
Or the 68-95% that the quality of Kocide SD addition is Waste Sulfuric Acid quality.
6. the method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation according to claim 1 prepares copper sulphate,
It is characterized in that：The redox reaction condition is reaction temperature at 30-80 DEG C, reaction time 30-180min.
7. the side of copper sulphate is prepared according to any lignocellulosic ester catalysis processing waste sulfuric acid from alkylation of claim 4-6
Method, it is characterised in that：The faintly acid pH value is 2.0-4.0.
8. the method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation according to claim 1 prepares copper sulphate,
It is characterized in that：Organic compost, which is carried out, after the leached mud and the mixing of cellulosic filter residue obtains degradable organic fertilizer base-material.
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