CN105480998B - A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares aluminum sulfate - Google Patents
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares aluminum sulfate Download PDFInfo
- Publication number
- CN105480998B CN105480998B CN201510946136.6A CN201510946136A CN105480998B CN 105480998 B CN105480998 B CN 105480998B CN 201510946136 A CN201510946136 A CN 201510946136A CN 105480998 B CN105480998 B CN 105480998B
- Authority
- CN
- China
- Prior art keywords
- sulfuric acid
- lignocellulosic ester
- acid
- waste sulfuric
- alkylation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/68—Aluminium compounds containing sulfur
- C01F7/74—Sulfates
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Fertilizers (AREA)
- Catalysts (AREA)
Abstract
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares aluminum sulfate, waste sulfuric acid from alkylation is added in aluminum oxide or aluminium hydroxide and reacted, is faintly acid to its pH value, obtains mixed liquor, 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 technical grade sulfuric acid aluminium product can be obtained after finally refined liquid is crystallized.Lignocellulosic ester selected by the present invention not only has catalysis, but also has active oxidation agent and adsorption bleaching function；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, and does not interfere with product quality, and product quality reaches the quality standard of technical grade；Simple in production process operation, atmospheric operation, securely and reliably, reduced investment；Lignocellulosic ester catalyst is biodegradable, can be as the raw material of bio-feritlizer, production process three-waste free discharge.
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 aluminum sulfate.
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 increase., 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 produce 1 ton of gasoline alkylate and just produce 80~100kg Waste Sulfuric Acids, 90% or so sulfuric acid is 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
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 it is huge to handle the costly of Waste Sulfuric Acid per ton, loss,
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, utilize 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 have stronger penetrating odor, it is difficult to the product of high-purity is obtained, and
The inorganic agent of addition easily causes 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 faced the risk of stopping production, and this will bring huge economic damage to enterprise
Lose.
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 suspension 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 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 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: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
After oxidant and activated carbon are added in liquid and stirs decolouring, 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 well mixed, in 700-1100
After being calcined at DEG C, it 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 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 aluminum sulfate, waste residue, refined liquid after this method processing have no irritating odor, and refined liquid is as clear as crystal, refined liquid
The aluminum sulfate 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 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 aluminum sulfate, by waste sulfuric acid from alkylation plus
Enter into aluminum oxide or aluminium hydroxide and react, be faintly acid to its pH value, obtain mixed liquor, mixed liquor is filtrated to get leached mud
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, obtain
To cellulosic filter residue and refined liquid, technical grade sulfuric acid aluminium product is can obtain after finally refined liquid is crystallized.
The method that above-described lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares aluminum sulfate, 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 100：5-40：1-8 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
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, after reaching 0.5-1.5h soak times, stop stirring, take out esterification products and abrading-ball, and they are separated, obtain wooden fibre
Tie up plain ester admixture；
(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 aluminum 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 aluminum sulfate, it is described
Auxiliary agent is catalyst for esterification reaction, and described catalyst for esterification reaction is aluminium salt, and described aluminium salt is AlCl3、Al(NO3)3、Al2
(SO4)3In one or two kinds of mixture.
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 aluminum 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 aluminum sulfate, described catalysis
The quality that agent and oxidant add is respectively the 0.2-5% and 1-20% of Waste Sulfuric Acid quality, what aluminum oxide or aluminium hydroxide added
Quality is the 25-50% of Waste Sulfuric Acid quality.
The method that above-described lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares aluminum sulfate, the oxidation is also
Former reaction condition be 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 aluminum sulfate, it is described
Faintly acid pH value is 1.0-3.0.
The method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation described in any of the above prepares aluminum 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., have catalysis, the function of active oxidation, and energy catalytic oxidant produces the living radical or original of strong oxidizing property
Sub- oxygen, make oxidant activation, accelerate reactant degraded, meanwhile, catalyst accelerates oxygen atom in system by effects such as complexings
Transmission, equally enhance system oxidation.Cellulosic filter residue and refined liquid after this method processing have no irritating odor,
Refined liquid is as clear as crystal.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, oxidant is reacted rapidly and decomposite active group (free radical), and then oxidation Decomposition is organic
Thing, final product CO2、H2O and N2Deng innocuous substance, separation of solid and liquid obtains cellulosic filter residue and refined liquid, finally will be refined
Technical grade sulfuric acid aluminium product is can obtain after liquid crystallization.And although the purity for the aluminum sulfate that prior art is prepared can reach
Technical grade, but outward appearance is poor, and have penetrating odor.
(2) the lignocellulosic ester selected by the present invention also has adsorption bleaching function simultaneously, can select to adsorb heavy metal
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 catalyst of the aluminium salt as esterification in the preparation,
Effectively reduce the introducing of other chemical impurities so that the purity of finally prepd aluminum 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 after through separation of solid and liquid and being desorbed heavy metal ion
With bio-fertilizer raw material.
(7) 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, it is easy to operate.Particularly apply and varied without in existing Waste Water Treatment
Originally handling process, can directly it apply.
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 butanedioic acid and auxiliary agent A lCl3 are pressed 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 adds
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：By cellulosic solid waste powder, esterifying agent maleic acid and auxiliary agent A l (NO3)3By 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 adds
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：By cellulosic solid waste powder, esterifying agent oxalic acid and auxiliary agent A l2(SO4)3By 100：15：3 ratio
Example 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 adds
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 (AlCl3、Al(NO3)3By any
The mixture of ratio mixing) press 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 adds
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：By cellulosic solid waste powder, esterifying agent butyric acid and auxiliary agent (AlCl3、、Al2(SO4)3By any
The mixture of ratio mixing) press 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 adds
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 (Al (NO3)3、Al2(SO4)3Press
The mixture of arbitrary proportion mixing) press 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 adds
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 A lCl3 are pressed 100：35：7 ratio
Example 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 adds
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：By cellulosic solid waste powder, esterifying agent caprylic acid and auxiliary agent A l (NO3)3By 100：40：8
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:550ml ratio adds
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 40 mesh sieves；
(2) mixed at high speed：By cellulosic solid waste powder, esterifying agent laurate and auxiliary agent A l2(SO4)3By 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 adds
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 method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares aluminum sulfate, it is by mass concentration
90.5% waste sulfuric acid from alkylation, which is added in 30% aluminum oxide of Waste Sulfuric Acid quality, to react, to its pH value be 1 be reaction eventually
Point, obtains mixed liquor, and mixed liquor is filtrated to get to the reaction solution of leached mud and black；Then embodiment 1 is added in reaction solution
The quality that prepared catalyst lignocellulosic ester and oxidant (hydrogen peroxide), catalyst and oxidant add is respectively sulfur waste
The 0.2% of sour quality and 20%, redox reaction, reaction time 30min occur under the conditions of 30 DEG C in reaction temperature, you can
Organic matter in waste sulfuric acid from alkylation is fully converted to CO2、H2O、N2Etc. harmless small-molecule substance, separation of solid and liquid, fiber is obtained
Matter filter residue and as clear as crystal refined liquid, finally refined liquid is crystallized, centrifuged, purity is can obtain after drying up to industry
The aluminum sulfate product of level or feed grade, product is pure white, has no irritating odor.Carried out after leached mud and the mixing of cellulosic filter residue organic
Compost obtains degradable organic fertilizer base-material.
Embodiment 11
A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares aluminum sulfate, 91% alkylation is given up
Sulfuric acid, which is added in 45% aluminium hydroxide of Waste Sulfuric Acid quality, to react, and it 1.2 is reaction end to be to its pH value, is mixed
Liquid, mixed liquor is filtrated to get to 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 add 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, cellulosic filter residue and limpid is obtained
Transparent refined liquid, finally refined liquid is crystallized, centrifuged, dry after can obtain purity up to technical grade or feed grade
Aluminum sulfate product, 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 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 aluminum sulfate, by 91.5% alkylation
Waste Sulfuric Acid, which is added in 32% aluminum oxide of Waste Sulfuric Acid quality, to react, and it 1.4 is reaction end to be to its pH value, is mixed
Liquid, mixed liquor is filtrated to get to 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 add 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, cellulosic filter residue and limpid is obtained
Bright refined liquid, finally refined liquid is crystallized, centrifuged, can obtain purity up to technical grade or the sulphur of feed grade after drying
Sour aluminium product, 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 aluminum sulfate, 92% alkylation is given up
Sulfuric acid, which is added in 47% aluminium hydroxide of Waste Sulfuric Acid quality, to react, and it 1.8 is reaction end to be to its pH value, is mixed
Liquid, mixed liquor is filtrated to get to 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 add 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, cellulosic filter residue and limpid is obtained
Transparent refined liquid, finally refined liquid is crystallized, centrifuged, dry after can obtain purity up to technical grade or feed grade
Aluminum sulfate product, 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 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 aluminum sulfate, by 92.5% alkylation
Waste Sulfuric Acid, which is added in 34% aluminum oxide of Waste Sulfuric Acid quality, to react, and it 2.2 is reaction end to be to its pH value, is mixed
Liquid, mixed liquor is filtrated to get to 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 add 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, cellulosic filter residue and limpid is obtained
Transparent refined liquid, finally refined liquid is crystallized, centrifuged, dry after can obtain purity up to technical grade or feed grade
Aluminum sulfate product, 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 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 aluminum sulfate, 93% alkylation is given up
Sulfuric acid, which is added in 48% aluminium hydroxide of Waste Sulfuric Acid quality, to react, and it 2.6 is reaction end to be to its pH value, is mixed
Liquid, mixed liquor is filtrated to get to the reaction solution of leached mud and black；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 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, cellulosic filter residue and limpid is obtained
Bright refined liquid, finally refined liquid is crystallized, centrifuged, can obtain purity up to technical grade or the sulphur of feed grade after drying
Sour aluminium product, 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 aluminum sulfate, 95% alkylation is given up
Sulfuric acid, which is added in 50% aluminium hydroxide of Waste Sulfuric Acid quality, to react, and it 3.0 is reaction end to be to its pH value, is mixed
Liquid, mixed liquor is filtrated to get to 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 add 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, cellulosic filter residue and limpid is obtained
Bright refined liquid, finally refined liquid is crystallized, centrifuged, can obtain purity up to technical grade or the sulphur of feed grade after drying
Sour aluminium product, 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 (6)
1. a kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares aluminum sulfate, it is characterised in that：By alkyl
Change Waste Sulfuric Acid, which is added in aluminum oxide or aluminium hydroxide, to react, and is faintly acid to its pH value, 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, obtains fibre
Matter filter residue and refined liquid are tieed up, technical grade sulfuric acid aluminium product is can obtain after finally refined liquid is crystallized；Described 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 100：5-40：1-8 ratio is added to mixer
It is well mixed, obtain mixture；
(3) mechanical activation solid phase reaction：By said mixture grinding media heap volume according to 100g:200-600mL ratio adds
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-process：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 aluminium salt to answer catalyst, and described aluminium salt is AlCl3、Al(NO3)3、Al2(SO4)3In one or two kinds of mixture.
2. the method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation according to claim 1 prepares aluminum 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 aluminum sulfate, its
It is characterised by：The quality that described catalyst and oxidant add is respectively the 0.2-5% and 1-20% of Waste Sulfuric Acid quality, is aoxidized
The quality that aluminium or aluminium hydroxide add is the 25-50% of Waste Sulfuric Acid quality.
4. the method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation according to claim 1 prepares aluminum sulfate, its
It is characterised by：The redox reaction condition be reaction temperature at 30-80 DEG C, reaction time 30-180min.
5. the side of aluminum 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 faintly acid is that pH value is 1-3.
6. the method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation according to claim 1 prepares aluminum 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510946136.6A CN105480998B (en) | 2015-12-17 | 2015-12-17 | A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares aluminum sulfate |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510946136.6A CN105480998B (en) | 2015-12-17 | 2015-12-17 | A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares aluminum sulfate |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105480998A CN105480998A (en) | 2016-04-13 |
| CN105480998B true CN105480998B (en) | 2018-02-23 |
Family
ID=55668333
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510946136.6A Active CN105480998B (en) | 2015-12-17 | 2015-12-17 | A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares aluminum sulfate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105480998B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107792836B (en) * | 2016-08-31 | 2020-01-10 | 中国石油化工股份有限公司 | Regeneration method and device of alkylation waste sulfuric acid |
| CN108862208B (en) * | 2018-08-27 | 2022-10-25 | 青岛惠城信德新材料研究院有限公司 | Method for treating waste sulfuric acid discharged in alkylation production process |
| CN110639612B (en) * | 2019-10-09 | 2021-09-07 | 齐鲁工业大学 | Preparation method of magnetic nano cellulose fiber with catalytic degradation of 4-nitrophenol |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103435702A (en) * | 2013-07-26 | 2013-12-11 | 广西大学 | Cellulose higher fatty acid ester and preparation method thereof |
| CN103771353A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Regeneration method for alkylated waste sulfuric acid |
| CN104016385A (en) * | 2014-05-18 | 2014-09-03 | 天津理工大学 | Method for preparing magnesium sulfate and magnesium silico calcium sulfur fertilizer by utilizing alkylated waste sulfuric acid |
| CN105000536A (en) * | 2015-07-03 | 2015-10-28 | 青岛奥盖克化工股份有限公司 | Recycling technology of alkylate oil waste sulfuric acid |
-
2015
- 2015-12-17 CN CN201510946136.6A patent/CN105480998B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103771353A (en) * | 2012-10-24 | 2014-05-07 | 中国石油化工股份有限公司 | Regeneration method for alkylated waste sulfuric acid |
| CN103435702A (en) * | 2013-07-26 | 2013-12-11 | 广西大学 | Cellulose higher fatty acid ester and preparation method thereof |
| CN104016385A (en) * | 2014-05-18 | 2014-09-03 | 天津理工大学 | Method for preparing magnesium sulfate and magnesium silico calcium sulfur fertilizer by utilizing alkylated waste sulfuric acid |
| CN105000536A (en) * | 2015-07-03 | 2015-10-28 | 青岛奥盖克化工股份有限公司 | Recycling technology of alkylate oil waste sulfuric acid |
Non-Patent Citations (1)
| Title |
|---|
| "木质纤维素基碳质固体酸催化剂的制备及催化性能研究";王春雷等;《第11届固体化学与无机合成会议暨第二届道尔顿交易国际研讨会论文集》;20101114;第63-64页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105480998A (en) | 2016-04-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105480998B (en) | A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares aluminum sulfate | |
| CN104229852B (en) | A kind of carbide slag prepares the surface modifying method of fine calcium carbonate | |
| CN113620331B (en) | CO (carbon monoxide)2Method for preparing nanosphere aragonite calcium carbonate by mineralizing carbide slag | |
| CN104016385A (en) | Method for preparing magnesium sulfate and magnesium silico calcium sulfur fertilizer by utilizing alkylated waste sulfuric acid | |
| CN102491402A (en) | Method for producing refined copper oxide by utilizing acidic waste etching solution | |
| CN105540642B (en) | A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares zinc sulfate | |
| CN103864620A (en) | Production method of trioctyl trimellate | |
| CN105600826B (en) | A kind of method that lignocellulosic ester catalysis treatment waste sulfuric acid from alkylation prepares manganese sulfate | |
| CN105399963B (en) | A kind of mechanical activation method for preparing solid phase of lignocellulosic ester group oxidation catalyst | |
| CN105502309B (en) | A kind of method of lignocellulosic ester catalysis processing waste sulfuric acid from alkylation | |
| CN105502444B (en) | A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares magnesium sulfate | |
| CN105565363B (en) | A kind of method that lignocellulosic ester catalysis processing waste sulfuric acid from alkylation prepares copper sulphate | |
| CN106745113A (en) | A kind of method that biomass cellulose ester catalysis treatment waste sulfuric acid from alkylation prepares magnesium sulfate and fertiliser containing magnesium | |
| CN1063730C (en) | Technology for producing magnesium sulfate in treatment of titanium white waste sulfuric acid | |
| CN103642051A (en) | Method for treating alkali absorbed sulfur dioxide waste liquid by using lignin | |
| CN101823730A (en) | Method for simultaneously producing sodium thiocyanate and ammonium carbonate | |
| CN105384184A (en) | Method for preparing alum from mother solution produced by activated clay | |
| CN112456545A (en) | Method for preparing sodium stannate trihydrate by using tin stripping waste liquid | |
| CN1153764A (en) | Pinene esterifying and saponifying process synthesizing borneol and composite boron-titanium based catalyst | |
| CN103214053B (en) | Method for treating wastewater from gallic acid production | |
| CN111850672A (en) | Method for producing basic magnesium sulfate whisker by using alkylation waste sulfuric acid | |
| CN1207212C (en) | Production of potassium containing chemical products from waste liquid of molasses alcohol production | |
| DE1592159B2 (en) | PROCESS FOR CLARIFYING TECHNICAL SODIUM ALUMINATE SOLUTIONS FROM THE ALKALINE DIGESTION OF BAUXITES | |
| CN111439765A (en) | Decalcification method for producing magnesium hydroxide suspension and application thereof | |
| CN105693505A (en) | Treatment method of 1,4-dihydroxyanthraquinone industrial wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |