CN105502444B - A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares magnesium sulfate - Google Patents
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares magnesium sulfate Download PDFInfo
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- CN105502444B CN105502444B CN201510951586.4A CN201510951586A CN105502444B CN 105502444 B CN105502444 B CN 105502444B CN 201510951586 A CN201510951586 A CN 201510951586A CN 105502444 B CN105502444 B CN 105502444B
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F5/00—Compounds of magnesium
- C01F5/40—Magnesium sulfates
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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
- C05F5/00—Fertilisers from distillery wastes, molasses, vinasses, sugar plant or similar wastes or residues, e.g. from waste originating from industrial processing of raw material of agricultural origin or derived products thereof
- C05F5/002—Solid waste from mechanical processing of material, e.g. seed coats, olive pits, almond shells, fruit residue, rice hulls
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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
- C05F5/00—Fertilisers from distillery wastes, molasses, vinasses, sugar plant or similar wastes or residues, e.g. from waste originating from industrial processing of raw material of agricultural origin or derived products thereof
- C05F5/006—Waste from chemical processing of material, e.g. diestillation, roasting, cooking
- C05F5/008—Waste from biochemical processing of material, e.g. fermentation, breweries
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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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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/80—Compositional purity
Abstract
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares magnesium sulfate, waste sulfuric acid from alkylation is added in magnesia or magnesium hydroxide and reacted, and is that neutrality obtains mixed liquor to its pH value, mixed liquor is filtrated to get into 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 magnesium products of feed grade.Selected lignocellulosic ester of the invention has catalysis, active oxidation agent and adsorption bleaching function；Production process does not introduce other impurity, does not result in the organic matter in secondary pollution, spent acid and obtains oxidative degradation, mother liquor is all recycled, and does not interfere with product quality, and product quality reaches feed grade or the quality standard of technical grade.
Description
Technical field
The invention belongs to treatment of Organic Wastewater field, specifically a kind of lignocellulosic ester should as oxidation catalyst
Method for handling waste sulfuric acid from alkylation and preparing magnesium sulfate.
Background technology
Raising with the world to fuel demand, the current widely used alkylation process production isooctane of oil plant, yield flies
Speed increase.When processing high-octane gasoline alkylate with alkyl plant, need to concentration for 98% sulfuric acid as urging
Agent, often produces 1 ton of gasoline alkylate and just produces in 80~100kg Waste Sulfuric Acids, Waste Sulfuric Acid containing 90% or so sulfuric acid, 7% left side
Right organic matter and 3% or so water.Organic matter is mainly macromolecule alkene, alkadienes, alkyl sulfonic acid, sulfuric ester and vulcanization
Thing etc., these material colors are deep, quality is sticky, Odor stimulation, it is difficult to thoroughly be removed from sulfuric acid.Existing ripe treatment technology
Mainly pyrolysis recycle is into sulfuric acid reuse, but equipment investment is huge, and processing Waste Sulfuric Acid per ton it is costly, lose it is huge,
This cost and environment to manufacturing enterprise brings great pressure, is the biggest problem for perplexing enterprise's production.Other have extraction
Etc. handling process, but extractant cost recovery is high, sulfuric acid content is low, there is not yet there is the enterprise of application.In addition, utilizing alkyl
Changing Waste Sulfuric Acid production ammonium sulfate, magnesium sulfate, atlapulgite, precipitated silica, oil antirust agent etc. also has research, but due to can not
Organic matter effectively in degraded removing Waste Sulfuric Acid, product has stronger penetrating odor, it is difficult to obtain the product of high-purity, and
The inorganic agent of addition easily causes secondary pollution, and mother liquor is difficult to recycle.Therefore, current waste sulfuric acid from alkylation still cannot
Effectively processing, largely overstocks in manufacturing enterprise, enterprise is faced the risk of stopping production, and this will bring huge economic damage to enterprise
Lose.
Chinese patent title:A kind of method of utilization waste sulfuric acid from alkylation production magnesium sulfate and silico-calcium kieserite；Application is (specially
Profit) number:CN201410207898.X；The applying date:2014.05.18；Open (bulletin) number:CN104016385A；Open (bulletin)
Day:2014.09.03；The method of a kind of utilization waste sulfuric acid from alkylation production magnesium sulfate of the disclosure of the invention and silico-calcium kieserite, leads to
Production magnesium sulfate consumption sulfuric acid is crossed, goes out acid-soluble oil waste residue using the suspension adsorbing separation such as silicon, calcium in miberal powder, using containing the dregs of fat
The heat auxiliary external heat source calcining waste residue of heat and waste active carbon, makes organic carbon, production mainly contains silicon-calcium-magnesium sulphur
Fertilizer.The beneficial effects of the invention are as follows：This method technique is simple, easy to operate, easy to implement, and equipment investment is few, cost
Low, non-secondary pollution, the byproduct silico-calcium kieserite market demand are big, economic and social benefit 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:One kind is 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
Oxidant and activated carbon are added in liquid and is stirred after decolouring, press filtration again obtains refinement mother liquor and activated carbon waste residue, refinement mother liquor
By crystallization, centrifugation, drying, epsom salt is made；3) waste residue and activated carbon waste residue are well mixed, in 700-1100
After being calcined at DEG C, 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 is decolourized from activated carbon, the easy adsorption saturation of activated carbon, is decolourized often not thorough.
The content of the invention
For above-mentioned problem, the present invention develops a kind of lignocellulosic ester catalysis processing waste sulfuric acid from alkylation system
The method of standby magnesium sulfate, the waste residue and liquid after this method processing has no irritating odor, and waste liquid is as clear as crystal, after waste liquid is crystallized
The magnesium sulfate of high-purity is obtained, obtains degradable as organic compost is carried out after leached mud and cellulosic the filter residue mixing of discarded object
Organic fertilizer base-material.
The concrete technical scheme of the present invention is as follows：
The method that a kind of lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares magnesium sulfate, by waste sulfuric acid from alkylation plus
Enter into magnesia or magnesium hydroxide reaction, to its pH value for neutrality, obtain mixed liquor, by mixed liquor be filtrated to get leached mud and
The reaction solution of black；Then catalyst lignocellulosic ester is added in reaction solution and redox reaction occurs for oxidant, will
Organic matter in waste sulfuric acid from alkylation is CO by deep oxidation Degradation and Transformation2、H2O、N2Etc. harmless small-molecule substance, solid-liquid point
From obtaining cellulosic filter residue and as clear as crystal refined liquid, purity can obtain after finally refined liquid is crystallized up to technical grade
Or the sulfuric acid magnesium products of feed grade.
The method that above-described lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares magnesium sulfate, described is wooden
Cellulose esters preparation method comprises the following steps：
(1) pretreatment of raw material：Cellulosic solid waste is dried, crushing obtains cellulosic solid waste powder；
(2) mixed at high speed：By cellulosic solid waste powder, esterifying agent and auxiliary agent 100：5-40：1-8 ratio is added to
Mixer is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:200-600ml ratio
Add 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, reach after 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 magnesium sulfate, described esterification
Agent is carboxylic acid, and described carboxylic acid includes butanedioic acid, maleic acid, oxalic acid, citric acid, butyric acid, glycolic, amino acid, just pungent
Acid, any or two or more combination of laurate.
The method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation described in any of the above prepares magnesium sulfate, it is described
Auxiliary agent is catalyst for esterification reaction, and described catalyst for esterification reaction is magnesium salts, and described magnesium salts is MgCO3、Mg(NO3)2、
MgSO4, one or two kinds of thing mixed above in magnesium acetate.
According to Changshu of those of ordinary skill in the art, described cellulosic solid waste is bagasse, cassava grain stillage, cassava
Any or two or more combination of bar, wood chip, bamboo scraps, stalk, ramulus mori.Described drying is to dry cellulosic solid waste
It is less than 15% to water content, described crushing is that cellulosic solid waste was crushed into 20-60 mesh sieves.
The method that above-described lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares magnesium sulfate, described 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 magnesium sulfate, described catalysis
The quality that agent and oxidant are added is respectively the 0.2-5% and 1-20% of Waste Sulfuric Acid quality, what magnesia or magnesium hydroxide were added
Quality is the 35-60% of Waste Sulfuric Acid quality.
The method that above-described lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares magnesium sulfate, the oxidation is also
Former reaction condition is reaction temperature in 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 magnesium sulfate, it is described
PH neutral is 6.8-7.2.
The method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation described in any of the above prepares magnesium sulfate, its feature
It is：Organic compost, which is carried out, after leached mud and cellulosic the filter residue mixing obtains degradable organic fertilizer base-material.
The technique effect and advantage of the present invention：
(1) a large amount of acid or basic group, particularly hydroxyl, phenol are contained in the lignocellulosic ester surface selected by the present invention
Hydroxyl, carboxyl etc., the function with catalysis, active oxidation, energy catalytic oxidant produce the living radical or original of strong oxidizing property
Sub- oxygen, makes oxidant activation, accelerates reactant degraded, meanwhile, catalyst accelerates oxygen atom in system by the effect such as complexing
Transmission, equally enhance system oxidation.Cellulosic filter residue and refined liquid after this method processing have no irritating odor,
Refined liquid is limpid transparent.Existing technology can not it is fully effective degraded 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 urged
Agent, under its catalytic action, makes oxidant react rapidly and decomposites active group (free radical), and then oxidation Decomposition is organic
Thing, final product is CO2、H2O、N2Etc. harmless small-molecule substance, separation of solid and liquid obtains cellulosic filter residue and refined liquid, finally will
Purity is can obtain up to technical grade or the sulfuric acid magnesium products of feed grade after refined liquid crystallization, and product is pure white, nonirritant gas
Taste.Although and the purity for the magnesium sulfate that prior art is prepared can reach technical grade, not reaching feed grade, while outside
Sight is poor, and has penetrating odor.
(2) the lignocellulosic ester selected by the present invention also has adsorption bleaching function simultaneously, can select Adsorption of Heavy Metals
With raising decolorizing effect.
(3) the lignocellulosic ester selected by the present invention is free of heavy metal, is not in the secondary of leaching ability of heavy metal institute band
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 magnesium salts as the catalyst of esterification in the preparation,
Effectively reduce the introducing of other chemical impurities so that the purity of finally prepd magnesium sulfate 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 technology letter
Single, cost is low, and addition is few, therefore catalyst does not consider to reuse, and can make through separation of solid and liquid and after being desorbed heavy metal ion
Use bio-fertilizer raw material.
(7) it can be carried out at ambient pressure using the lignocellulosic ester catalysis organic wastewater oxidative degradation selected by the present invention,
The oxidative degradation device with stirring is only needed to, it is easy to operate.Particularly apply and varied without in existing Waste Water Treatment
Originally handling process, can directly be applied.
Embodiment
The preparation of lignocellulosic ester catalyst
Embodiment 1
The preparation of lignocellulosic ester catalyst, the preparation method comprises 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：By cellulosic solid waste powder, esterifying agent butanedioic acid and auxiliary agent MgCO3By 100：5：1 ratio
It is added to mixer to be well mixed, obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:200ml ratio is added
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, 0.5h is reached
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 comprises 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：By cellulosic solid waste powder, esterifying agent maleic acid and auxiliary agent Mg (NO3)2By 100：10：2
Ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:250ml ratio is added
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, 0.6h is reached
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 comprises 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：By cellulosic solid waste powder, esterifying agent oxalic acid and auxiliary agent MgSO4By 100：15：3 ratio
It is added to mixer to be well mixed, obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:300ml ratio is added
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, 0.7h is reached
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 comprises 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 C4H6O4Mg (magnesium acetate) is pressed
100：20：4 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:350ml ratio is added
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, 0.8h is reached
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 comprises 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：By cellulosic solid waste powder, esterifying agent butyric acid and auxiliary agent MgCO3With Mg (NO3)2By any ratio
The mixture of example mixing presses 100：25：5 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:400ml ratio is added
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, 0.9h is reached
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 comprises 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 agent3MgSO4And C4H6O4Mg (acetic acid
Magnesium) mixture that mixes in any proportion is by 100：30：6 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:450ml ratio is added
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, 1.0h is reached
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 comprises 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：By cellulosic solid waste powder, esterifying agent glycolic and auxiliary agent MgCO3And MgSO4By any ratio
The mixture of example mixing presses 100：35：7 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:500ml ratio is added
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, 1.1h is reached
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 comprises the following steps：
(1) pretreatment of raw material：Cellulosic solid waste drying to the water content that bagasse, cassava grain stillage are mixed is less than
10%th, the cellulosic solid waste powder for obtaining 60 mesh sieves is crushed；
(2) mixed at high speed：By cellulosic solid waste powder, esterifying agent caprylic acid and auxiliary agent MgCO3、Mg(NO3)2、MgSO4
And C4H6O4The mixture that Mg (magnesium acetate) is mixed in any proportion is by 100：40：8 ratio is added to mixer and is well mixed,
Obtain mixture；
(3) mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:550ml ratio is added
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, 1.2h is reached
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 comprises the following steps：
(1) pretreatment of raw material：Cellulosic solid waste drying to the water content that Cassava stalk, stalk, ramulus mori are mixed is less than
15%th, the cellulosic solid waste powder for obtaining 40 mesh sieves is crushed；
(2) mixed at high speed：By cellulosic solid waste powder, esterifying agent laurate and auxiliary agent MgCO3、Mg(NO3)2、MgSO4
The mixture mixed in any proportion is by 100：20：2 ratio is added to mixer and is well mixed, and obtains mixture；
(3) mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:300ml ratio is added
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, 1.5h is reached
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 method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares magnesium sulfate, be by mass concentration
90.5% waste sulfuric acid from alkylation, which is added in 37% magnesia of Waste Sulfuric Acid quality, to react, and it 6.8 is reaction to be to its pH value
Terminal, obtains mixed liquor, and mixed liquor is filtrated to get 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 are added 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, centrifuged, dry after can obtain purity up to work
The sulfuric acid magnesium products of industry level or feed grade, product is pure white, have 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 magnesium sulfate, 91% alkylation is given up
Sulfuric acid, which is added in 53% magnesium hydroxide of Waste Sulfuric Acid quality, to react, and it 6.9 is reaction end to be to its pH value, is mixed
Liquid, mixed liquor is filtrated to get the reaction solution of leached mud and black；Then the catalysis prepared by embodiment 2 is added in reaction solution
The quality that agent lignocellulosic ester and oxidant (air), catalyst and oxidant are added 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, centrifuged, dry after can obtain purity up to technical grade or feed grade
Sulfuric acid magnesium products, product is pure white, have no irritating odor.Organic compost is carried out after leached mud and the mixing of cellulosic filter residue to obtain dropping
The organic fertilizer base-material of solution.
Embodiment 12
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares magnesium sulfate, by 91.5% alkylation
Waste Sulfuric Acid, which is added in 40% magnesia of Waste Sulfuric Acid quality, to react, and it 7.0 is reaction end to be to its pH value, is mixed
Liquid, mixed liquor is filtrated to get the reaction solution of leached mud and black；Then the catalysis prepared by embodiment 3 is added in reaction solution
The quality that agent lignocellulosic ester and oxidant (oxygen), catalyst and oxidant are added 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, centrifuged, dry after can obtain purity up to technical grade or feed grade
Sulfuric acid magnesium products, product is pure white, have no irritating odor.Organic compost is carried out after leached mud and the mixing of cellulosic filter residue to obtain dropping
The organic fertilizer base-material of solution.
Embodiment 13
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares magnesium sulfate, 92% alkylation is given up
Sulfuric acid, which is added in 56% magnesium hydroxide of Waste Sulfuric Acid quality, to react, and it 7.1 is reaction end to be to its pH value, is mixed
Liquid, mixed liquor is filtrated to get the reaction solution of leached mud and black；Then the catalysis prepared by embodiment 4 is added in reaction solution
The quality that agent lignocellulosic ester and oxidant (ozone), catalyst and oxidant are added 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, centrifuged, dry after can obtain purity up to technical grade or feed grade
Sulfuric acid magnesium products, product is pure white, have no irritating odor.Organic compost is carried out after leached mud and the mixing of cellulosic filter residue to obtain dropping
The organic fertilizer base-material of solution.
Embodiment 14
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares magnesium sulfate, by 92.5% alkylation
Waste Sulfuric Acid, which is added in 43% magnesia of Waste Sulfuric Acid quality, to react, and it 7.2 is reaction end to be to its pH value, is mixed
Liquid, mixed liquor is filtrated to get the reaction solution of leached mud and black；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 are added 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, centrifuged, dry after can obtain purity up to technical grade or feed grade
Sulfuric acid magnesium products, product is pure white, have no irritating odor.Organic compost is carried out after leached mud and the mixing of cellulosic filter residue to obtain dropping
The organic fertilizer base-material of solution.
Embodiment 15
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares magnesium sulfate, 93% alkylation is given up
Sulfuric acid, which is added in 54% magnesium hydroxide of Waste Sulfuric Acid quality, to react, and it 6.8 is reaction end to be to its pH value, is mixed
Liquid, mixed liquor is filtrated to get the reaction solution of leached mud and black；Then urging prepared by embodiment 6 is added in reaction solution
The quality that agent lignocellulosic ester and oxidant (air), catalyst and oxidant are added is respectively the 3% of Waste Sulfuric Acid quality
With 10%, redox reaction, reaction time 130min occur under the conditions of 60 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, centrifuged, dry after can obtain purity up to technical grade or feed grade
Sulfuric acid magnesium products, product is pure white, have no irritating odor.Organic compost is carried out after leached mud and the mixing of cellulosic filter residue to obtain dropping
The organic fertilizer base-material of solution.
Embodiment 16
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares magnesium sulfate, 95% alkylation is given up
Sulfuric acid, which is added in 60% magnesium hydroxide of Waste Sulfuric Acid quality, to react, and it 6.9 is reaction end to be to its pH value, is mixed
Liquid, mixed liquor is filtrated to get the reaction solution of leached mud and black；Then the catalysis prepared by embodiment 7 is added in reaction solution
The quality that agent lignocellulosic ester and oxidant (oxygen), catalyst and oxidant are added 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, centrifuged, dry after can obtain purity up to technical grade or the sulphur of feed grade
Sour magnesium products, product is pure white, have no irritating odor.Organic compost, which is carried out, after leached mud and the mixing of cellulosic filter residue obtains degradable
Organic fertilizer base-material.
Embodiment 17
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares magnesium sulfate, 89% alkylation is given up
Sulfuric acid, which is added in 37% magnesia of Waste Sulfuric Acid quality, to react, and it 7.0 is reaction end to be to its pH value, obtains mixed liquor,
Mixed liquor is filtrated to get 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 are added 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, centrifuged, dry after can obtain purity up to technical grade or the sulphur of feed grade
Sour magnesium products, product is pure white, have no irritating odor.Organic compost, which is carried out, after leached mud and the mixing of cellulosic filter residue obtains degradable
Organic fertilizer base-material.
Embodiment 18
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares magnesium sulfate, 85% alkylation is given up
Sulfuric acid, which is added in 35% magnesia of Waste Sulfuric Acid quality, to react, and it 7.1 is reaction end to be to its pH value, obtains mixed liquor,
Mixed liquor is filtrated to get 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 are added 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, centrifuged, dry after can obtain purity up to technical grade or the sulphur of feed grade
Sour magnesium products, product is pure white, have no irritating odor.Organic compost, which is carried out, after leached mud and the mixing of cellulosic filter residue obtains degradable
Organic fertilizer base-material.
Claims (6)
1. a kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares magnesium sulfate, it is characterised in that：By alkyl
Change Waste Sulfuric Acid and be added to reaction in magnesia or magnesium hydroxide, be neutrality to its pH value, obtain mixed liquor, mixed liquor is filtered
To leached mud and the reaction solution of black；Then catalyst lignocellulosic ester is added in reaction solution and oxidation occurs for oxidant also
Original reaction, CO is fully converted to by the organic matter in waste sulfuric acid from alkylation2、H2O、N2Harmless small-molecule substance, separation of solid and liquid is obtained
Purity is can obtain to cellulosic filter residue and refined liquid, after finally refined liquid is crystallized up to technical grade or the magnesium sulfate of feed grade
Product;Described lignocellulosic ester preparation method comprises the following steps：
（1）Pretreatment of raw material：Cellulosic solid waste is dried, crushing obtains cellulosic solid waste powder；
（2）Mixed at high speed：By cellulosic solid waste powder, esterifying agent and auxiliary agent 100：5-40：1-8 mass ratio is added to mixed
Conjunction machine is well mixed, and obtains mixture；
（3）Mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:200-600mL ratio is added
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;Described
Esterifying agent is carboxylic acid, described carboxylic acid include butanedioic acid, maleic acid, oxalic acid, citric acid, butyric acid, glycolic, amino acid,
Caprylic acid, any or two or more combination of laurate;Described auxiliary agent is catalyst for esterification reaction, and described esterification is anti-
It is magnesium salts to answer catalyst, and described magnesium salts is MgCO3、Mg(NO3)2、MgSO4, the one or two kinds of in magnesium acetate it is mixed above
Thing.
2. the method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation according to claim 1 prepares magnesium sulfate, its
It is characterised by：Described oxidant is one kind in air, oxygen, hydrogen peroxide and ozone.
3. the method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation according to claim 1 prepares magnesium sulfate, its
It is characterised by：The quality that described catalyst and oxidant are added is respectively the 0.2-5% and 1-20% of Waste Sulfuric Acid quality, magnesia
Or the 35-60% that the quality of magnesium hydroxide addition is Waste Sulfuric Acid quality.
4. the method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation according to claim 1 prepares magnesium sulfate, its
It is characterised by：The redox reaction condition is reaction temperature in 30-80 DEG C, reaction time 30-180min.
5. the side of magnesium sulfate is prepared according to any described lignocellulosic ester catalysis processing waste sulfuric acid from alkylation of claim 2-4
Method, it is characterised in that：Described pH neutral is 6.8-7.2.
6. the method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation according to claim 1 prepares magnesium sulfate, its
It is characterised by：Organic compost, which is carried out, after leached mud and cellulosic the filter residue mixing obtains degradable organic fertilizer base-material.
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