CN108707967A - A method of preparing calcium sulfate crystal whiskers using the sulfate radical in sour dead-wood quality black liquor - Google Patents
A method of preparing calcium sulfate crystal whiskers using the sulfate radical in sour dead-wood quality black liquor Download PDFInfo
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- CN108707967A CN108707967A CN201810919661.2A CN201810919661A CN108707967A CN 108707967 A CN108707967 A CN 108707967A CN 201810919661 A CN201810919661 A CN 201810919661A CN 108707967 A CN108707967 A CN 108707967A
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- Prior art keywords
- calcium sulfate
- crystal whiskers
- lignin
- sulfate crystal
- black liquor
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- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 title claims abstract description 123
- 239000013078 crystal Substances 0.000 title claims abstract description 62
- 238000000034 method Methods 0.000 title claims abstract description 36
- 239000002023 wood Substances 0.000 title claims abstract description 16
- 229920005610 lignin Polymers 0.000 claims abstract description 44
- 239000007788 liquid Substances 0.000 claims abstract description 39
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000000725 suspension Substances 0.000 claims abstract description 22
- 238000000926 separation method Methods 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 12
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 12
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 12
- 150000007524 organic acids Chemical class 0.000 claims abstract description 12
- 239000000292 calcium oxide Substances 0.000 claims abstract description 10
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 10
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 15
- 239000004744 fabric Substances 0.000 claims description 9
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 8
- 238000001354 calcination Methods 0.000 claims description 7
- 235000015165 citric acid Nutrition 0.000 claims description 6
- 239000001913 cellulose Substances 0.000 claims description 5
- 229920002678 cellulose Polymers 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 4
- 229920002488 Hemicellulose Polymers 0.000 claims description 4
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 4
- 239000004310 lactic acid Substances 0.000 claims description 4
- 235000014655 lactic acid Nutrition 0.000 claims description 4
- 239000001630 malic acid Substances 0.000 claims description 4
- 235000011090 malic acid Nutrition 0.000 claims description 4
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 3
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 3
- 235000005822 corn Nutrition 0.000 claims description 3
- 240000008042 Zea mays Species 0.000 claims 1
- 229920003023 plastic Polymers 0.000 abstract description 15
- 239000004033 plastic Substances 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 15
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000002425 crystallisation Methods 0.000 abstract description 2
- 230000008025 crystallization Effects 0.000 abstract description 2
- 229940095672 calcium sulfate Drugs 0.000 description 50
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 20
- -1 sulfate radical Chemical class 0.000 description 19
- 229920000915 polyvinyl chloride Polymers 0.000 description 17
- 239000004800 polyvinyl chloride Substances 0.000 description 17
- 230000008569 process Effects 0.000 description 14
- 239000007787 solid Substances 0.000 description 12
- 239000006228 supernatant Substances 0.000 description 11
- 238000001556 precipitation Methods 0.000 description 9
- 238000005452 bending Methods 0.000 description 8
- 239000000835 fiber Substances 0.000 description 7
- 238000001914 filtration Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000002360 preparation method Methods 0.000 description 6
- 239000000047 product Substances 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000004743 Polypropylene Substances 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 229920001155 polypropylene Polymers 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 229910052602 gypsum Inorganic materials 0.000 description 3
- 239000010440 gypsum Substances 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 230000002572 peristaltic effect Effects 0.000 description 3
- 239000010865 sewage Substances 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical group [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- ZFOZVQLOBQUTQQ-UHFFFAOYSA-N Tributyl citrate Chemical compound CCCCOC(=O)CC(O)(C(=O)OCCCC)CC(=O)OCCCC ZFOZVQLOBQUTQQ-UHFFFAOYSA-N 0.000 description 2
- 241000209149 Zea Species 0.000 description 2
- 229940095564 anhydrous calcium sulfate Drugs 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 150000005837 radical ions Chemical class 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 235000021355 Stearic acid Nutrition 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000012675 alcoholic extract Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- CJZGTCYPCWQAJB-UHFFFAOYSA-L calcium stearate Chemical compound [Ca+2].CCCCCCCCCCCCCCCCCC([O-])=O.CCCCCCCCCCCCCCCCCC([O-])=O CJZGTCYPCWQAJB-UHFFFAOYSA-L 0.000 description 1
- 239000008116 calcium stearate Substances 0.000 description 1
- 235000013539 calcium stearate Nutrition 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000001768 carboxy methyl cellulose Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004035 construction material Substances 0.000 description 1
- KYQODXQIAJFKPH-UHFFFAOYSA-N diazanium;2-[2-[bis(carboxymethyl)amino]ethyl-(carboxylatomethyl)amino]acetate Chemical compound [NH4+].[NH4+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O KYQODXQIAJFKPH-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 229910017053 inorganic salt Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 1
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical group OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 description 1
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 description 1
- 235000019832 sodium triphosphate Nutrition 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000008117 stearic acid Substances 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/10—Inorganic compounds or compositions
- C30B29/46—Sulfur-, selenium- or tellurium-containing compounds
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
- C30B29/60—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape characterised by shape
- C30B29/62—Whiskers or needles
-
- C—CHEMISTRY; METALLURGY
- C30—CRYSTAL GROWTH
- C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
- C30B7/00—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions
- C30B7/10—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions by application of pressure, e.g. hydrothermal processes
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Crystals, And After-Treatments Of Crystals (AREA)
Abstract
The invention discloses a kind of methods that the sulfate radical using in sour dead-wood quality black liquor prepares calcium sulfate crystal whiskers, include the following steps：(1) lignin suspension is filtered, obtains lignin black liquor, sulfuric acid is instilled into the lignin black liquor, adjust pH to 1.0~2.5；(2) system that step (1) obtains is separated by solid-liquid separation, takes gained liquid, calcium hydroxide or calcium oxide is added into the liquid, obtains precipitated liquid system；(3) organic acid is added into the precipitated liquid system, then carries out hydro-thermal process, obtain calcium sulfate crystal whiskers suspension；(4) the calcium sulfate crystal whiskers suspension is separated by solid-liquid separation, dried, calcined, obtain calcium sulfate crystal whiskers.The calcium sulfate crystal whiskers that the present invention is prepared are free of the crystallization water, have many advantages, such as that stability is good, draw ratio is big.Calcium sulfate crystal whiskers obtained by the present invention are applied in PVC plastic, it is found that the performance indicators such as plastic hardness are significantly improved.
Description
Technical field
It is the present invention relates to a kind of method preparing calcium sulfate crystal whiskers, more particularly to a kind of using in sour dead-wood quality black liquor
The method that sulfate radical prepares calcium sulfate crystal whiskers.
Background technology
Lignin is a kind of natural organic polymer compounds, in nature next in number only to cellulose, molecule
There are the functional groups such as alcoholic extract hydroxyl group, phenolic hydroxyl group, carbonyl, carboxyl, methoxyl group, sulfonic group in structure, and oxidation, sulfonation, alkane can occur
A variety of chemical reactions such as base, halogenation, nitrification, polycondensation, therefore in industries such as adhesive, plastics, construction material, coating, films
There is larger purposes.
Lignin in current industrial is mainly derived from the processing treatment industry of paper industry and stalk corncob.Due to wood
Containing acid functionals groups such as phenolic hydroxyl groups in quality molecular structure, therefore often exist in the form of ion in the solution.And in alkali
Property environment in, lignin exists in the form of anion, and solubility is larger, and under acid system, lignin is mostly with neutral or simultaneous
Property ion form exist, solubility drastically declines.Therefore, it no matter in paper industry or stalk corn processing industry, obtains
The method for obtaining lignin is mostly sulfuric acid sedimentation (CN200880127214.8, CN201610233203.4), adjusts terminal pH
Ranging from 1.0~3.0, then while obtaining lignin, inevitably introduces and generate a large amount of sulfate ion (waste liquids
Middle content is generally higher than 30g/L), bring very big difficulty for the processing of follow-up sewage.On the other hand, radical ion containing high-concentration sulfuric acid
Industrial wastewater direct emission can bring a series of harm to environment and the mankind, cause water body generate mineralization, be to cause
The main reason for water body permanent hardness index height and high salinity, endanger ecological environment.
Therefore, the process problem of sulfate ion seems extremely important in sour dead-wood quality black liquor, how to be provided to it
Sourceization utilizes, and not only contributes to solve environmental problem, and can obtain certain economic benefit.
Calcium sulfate crystal whiskers are also known as crystal whisker of gypsum, are important inorganic salt crystal, according to the more of crystals moisture
Three kinds of anhydrous, Ban Shui and two water, wherein the intensity highest of anhydrous calcium sulfate whisker can be divided into less.With other crystal phase ratios,
Calcium sulfate crystal whiskers have many advantages, such as can high temperature resistant, acid and alkali-resistance, good toughness, intensity is high, resist chemical, and price is in inorganic crystalline substance
It is relatively low in whisker material, there is higher cost performance.The application range of crystal whisker of gypsum is very extensive, be mainly used in paper industry,
In building materials industry, ceramic industry, mechanical industry and light industry.Currently, the method for preparing crystal whisker of gypsum has very much, different methods
Feature is different, and the most common are hydro-thermal methods.The preparation method of traditional calcium sulfate crystal whiskers is hydro-thermal method, and technique is relatively simple.And it is wooden
Containing impurity such as more cellulose, hemicellulose and inorganic salts in quality black liquor, ingredient is complex, such as existing silicate
Ion can generate competitive relation with sulfate radical, inhibit the growth rate of whisker end face in the forming process of calcium sulfate crystal whiskers,
And then inhibit the formation of whisker.Furthermore the large hydrophilic molecular contained in lignin black liquor is easy to generate with calcium sulfate crystal face
Interaction, influences conversion process of the calcium sulfate dihydrate to whisker, this prepares calcium sulfate crystal whiskers for hydro-thermal method and brings very
Big difficulty.
Invention content
Goal of the invention：In order to solve the above-mentioned problems in the prior art, sour dead-wood is utilized the present invention provides a kind of
The method that sulfate radical in quality black liquor prepares calcium sulfate crystal whiskers, this method not only alleviate the pressure of sewage disposal, also realize
The recycling of sulfate ion.
Technical solution：The method that sulfate radical of the present invention using in sour dead-wood quality black liquor prepares calcium sulfate crystal whiskers,
Include the following steps：
(1) lignin suspension is filtered, obtains lignin black liquor, sulfuric acid is instilled into the lignin black liquor,
PH to 1.0~3.0 is adjusted, lignin is made to settle；
(2) system that step (1) obtains is separated by solid-liquid separation, takes gained liquid, hydroxide is added into the liquid
Calcium or calcium oxide obtain precipitated liquid system；
(3) organic acid is added into the precipitated liquid system, then carries out hydro-thermal process, the temperature of hydro-thermal process is 150
~170 DEG C, the time of hydro-thermal process is 4~6h, obtains calcium sulfate crystal whiskers suspension；
(4) the calcium sulfate crystal whiskers suspension is separated by solid-liquid separation, dried, calcined, obtain calcium sulfate crystal whiskers.
In step (1), the lignin suspension is that the lignin that paper industry or stalk corn processing industry generate is outstanding
Supernatant liquid, main component have lignin, cellulose and hemicellulose, and wherein content of lignin is 18~25g/L.Lignin lacks
Measure cellulose and hemicellulose, pigment, inorganic salts etc..
In step (1), described be filtered into is filtered lignin suspension using 300 mesh and the above nylon-type filter cloth.
Due to containing more fiber fines in lignin suspension, there is small size, large specific surface area, structural form, chemical property not
One the features such as, can retain its fiber fines using 300 mesh and the above nylon-type filter cloth.
300 mesh and the above nylon-type filter cloth are preferably the polypropylene fibre filter cloth of 300 mesh.
In step (1), the lignin black liquor is first subjected to ultrasound, stirring, then instill sulfuric acid thereto.After instilling sulfuric acid
It is sufficiently stirred, lignin is made to be precipitated to the greatest extent.
In step (1), a concentration of 5~50wt% of the sulfuric acid used, preferably 20~40wt%.
In step (1), pH to 1.0~2.5 is preferably adjusted.
In step (2), the separation of solid and liquid can be dried obtained solid by way of centrifuging or filtering, for wood
Quality crude product.
In step (2), calcium hydroxide or calcium oxide is added until the pH of solution is 5.5~7.0.It is separated by solid-liquid separation gained liquid
In contain more sulfate ion, calcium hydroxide or calcium oxide, which is added, makes its generate calcium sulfate precipitation, and sulfate ion is made to obtain
Recycling.
In step (3), the organic acid is crystal modifier, and calcium sulfate precipitation can be promoted to turn to the direction of calcium sulfate crystal whiskers
Change, the organic acid is citric acid, lactic acid or malic acid, preferably citric acid, and the addition of the organic acid is precipitating liquid
It is the 0.1~0.5% of gross mass.
In step (3), the hydro-thermal process carries out in autoclave.
In step (3), drying temperature is 60~120 DEG C, 2~4h of drying time, and calcination temperature is 750~950 DEG C, calcining
Time is 3~4h.
The calcium sulfate precipitation in filtration step (2) is not needed, the preparation of whisker can be made to react directly in original system
It carries out, saves water consume.
It is highly preferred that the method that the sulfate radical of the present invention using in sour dead-wood quality black liquor prepares calcium sulfate crystal whiskers,
Including steps are as follows：
(1) the lignin suspension for taking paper industry to generate, is pre-processed first, more thin due to containing in suspension
Small fiber has the characteristics that small size, large specific surface area, structural form, chemical property differ, and nylon-type filter cloth 300 can be used
Mesh or more retains it, obtains lignin black liquor；
(2) the lignin black liquor that step (1) obtains is subjected to supersound process 10min, is then stirred, is opened at room temperature
Beginning is pumped into sulfuric acid dropwise, so that system pH is gradually reduced, when pH is down to 1.0~3.0, continues 1.5~2.5h of stirring, make lignin
Utmostly settle.Here used sulfuric acid, concentration is between 5~50wt%；
(3) liquid in (2) is separated by solid-liquid separation, it can be by way of centrifuging or filtering, solid is dried after centrifugation,
For lignin crude product.
(4) step (3) is separated by solid-liquid separation obtained supernatant, and containing more sulfate ion, being slowly added into calcium hydroxide makes
It is reacted with the sulfate ion in solution generates calcium sulfate precipitation, to remove the sulfate ion in supernatant.It can also make
Calcium hydroxide is replaced with calcium oxide.But it is both needed to the addition of control calcium hydroxide or calcium oxide so that the pH of system rises to 5.5
~7.0 be addition terminal.It should be pointed out that this step is not necessarily to temperature control.
(5) organic acid that addition mass fraction is 0.1%~0.5% in the precipitated liquid system of step (4), make by organic acid
For crystal modifier, calcium sulfate precipitation can be promoted to be converted to the direction of calcium sulfate crystal whiskers, addition needs to control, and excessive addition can increase
Add the cost for turning brilliant, very few addition that can influence the quality of product；In addition, it is necessary to be pointed out that organic acid be added is preferred
Citric acid, lactic acid, malic acid, more preferable citric acid.
(6) the solid-liquid mixed liquor for obtaining step (5), is placed in autoclave, directly carries out hydro-thermal process, and condition is
150~170 DEG C, 4~6h obtains calcium sulfate crystal whiskers suspension；
(7) the calcium sulfate crystal whiskers suspension of step (6) is separated by solid-liquid separation, the mode for centrifuging or filtering can be selected,
Precipitation can be washed with water or ethyl alcohol, to remove whisker surface impurity.Precipitation is then placed in 60~120 DEG C of baking oven, 2~
4h dries precipitation.It should be pointed out that the residual volume of sulfate ion is less than 1.4g/L in filtrate at this time.
(8) precipitation after drying in (7) is placed in 750~950 DEG C of high temperature furnace and calcines the obtained dead plasters of 3~4h
Crystal whisker products.
The optical microscope of calcium sulfate whiskers prepared by the present invention is as shown in Figure 1, X-ray powder diffraction spectrogram
As shown in Fig. 2, heat analysis TG-DSC spectrograms are as shown in figure 3, infrared spectrogram is as shown in Figure 4.By micro- sem observation and it is subject to
Measurement can show that obtained calcium sulfate whiskers draw ratio about 1: 30~90, whisker is more elongated, uniformly.Pass through X-
Ray powder diffractogram can be seen that gained whisker crystallinity it is very high, as Thermal Chart as can be seen that obtained by whisker
Without the crystallization water, product is stablized.
The present invention provides a kind of lignin black liquor generated using paper industry as raw material, utilizes the sulfuric acid in its supernatant
The method that radical ion prepares calcium sulfate crystal whiskers can make the sulfate ion of supernatant generate calcium sulfate to be carried out to it by reaction
Recycling, and anhydrous calcium sulfate whisker is obtained by hydro-thermal method, this not only alleviates the pressure of sewage disposal, also achieves sulfate radical
The recycling of ion.
Advantageous effect：Compared with the existing technology, the present invention has the following advantages：
1, the present invention effectively eliminates the sulfate ion in paper industry acid dead-wood quality black liquor, reduces follow-up dirt
The pressure of water process, while its recycling is successfully prepared calcium sulfate crystal whiskers, new added value of product can be formed.
2, during the present invention prepares calcium sulfate crystal whiskers using sulfate radical in sour dead-wood quality black liquor, black liquor can be utilized
Direct Hydrothermal convert, need not from the external world introduce water, water consume can be saved, it is easy to accomplish large-scale industrial production, have compared with
High economic value.
3, present invention firstly discovers that organic acid can be as the good crystal modifier for preparing calcium sulfate crystal whiskers so that calcium sulfate is heavy
Shallow lake still may be implemented well to turn crystalline substance under the Black Liquor System containing complicated ingredient.
4, the calcium sulfate crystal whiskers that the present invention is prepared are in PVC plastic material products, test result to be found to plastics
Performance is obviously improved.
Description of the drawings
Fig. 1 is calcium sulfate crystal whiskers optical microscope (16 × 10 times)；
Fig. 2 is calcium sulfate crystal whiskers X-ray powder diffraction spectrogram；
Fig. 3 is calcium sulfate crystal whiskers TG-DSC spectrograms；
Fig. 4 is calcium sulfate crystal whiskers infrared spectrogram.
Specific implementation mode
With reference to example, the present invention is further illustrated.
Whiteness test in following embodiment：Leucometer model：ZBD type leucometers；With reference to national standard：GB2913-82.
Comparative example 1, the PVC material bending property experimental result for being not added with calcium sulfate crystal whiskers
The preparation method of PVC plastic plank is as follows：Polyvinyl chloride 100g, calcium stearate 5g, tributyl citrate 3g, adjacent benzene
Dicarboxylic acid esters 3g, polyacrylamide 2g, sodium tripolyphosphate 3g, stearic acid 2g, dimethyl dimercapto 2-ethyl hexyl ethanoate tin 4g, modification
Auxiliary agent 13g；Wherein modified additive is magnesium chloride 5g, sodium carboxymethylcellulose 3g, b diammonium edta 2g, epoxy tetrahydrochysene neighbour benzene two
Formic acid dioctyl ester 3g.Above-mentioned sample is uniformly mixed, is placed in mixer and is kneaded 3 minutes, melting temperature is 140 DEG C, by feeding
Screw rod injects double screw extruder, is squeezed out through double screw extruder, after mold molding, sizing, then cuts off, obtains PVC plastic flitch.
Its bending property test result is shown in Table 1.
Embodiment 1
The lignin suspension for taking 2L paper industries to generate carries out vacuum filter using the polypropylene fibre filter cloth of 300 mesh, obtains wood
Quality black liquor.The black liquor of acquisition is subjected to ultrasound 10min, 5wt%H is pumped into dropwise using peristaltic pump2SO4, keep stirring in the process
It mixes, room temperature, adjusts pH to 2.5, lignin is made to settle, and pH is kept to continue to stir 2h not higher than 2.5；Then using hypervelocity
Centrifuge is separated by solid-liquid separation at 12000rpm, time 10min, is obtained the supernatant fluid containing more sulfate ion and (is surveyed
It is 30g/L to obtain sulfate radical content), it is slowly added to a small amount of calcium hydroxide solid powder, process holding is sufficiently stirred, and waits for that pH stablizes
Afterwards, calcium hydroxide powder is continuously added, until pH stablizes between 5.5~7.0, continues to stir 1h, it is made fully to react.Then
The lactic acid that mass fraction is 0.1% is added, after being sufficiently stirred, slurries are directly transferred in stainless steel autoclave, is arranged
Temperature in autoclave is at 150 DEG C.Process is kept stirring, and reacts 4h, and lower tank (is measured by filtering to be separated by solid-liquid separation
Sulfate ion concentration is 1.2g/L in supernatant, 96%) removal rate of sulfate ion reaches, and ethyl alcohol is used in combination to wash solid,
And be placed in 60 DEG C of baking ovens and be dried, after 2h, solid is transferred in 750 DEG C of high temperature furnace and carries out calcining 4h, then dropped
Calcium sulfate crystal whiskers are obtained to room temperature.It is 0.21g/ml, whiteness 85, draw ratio 1: 40~70, heat analysis to measure its bulk density
The result shows that its water content is 0.
The 10g calcium sulfate crystal whiskers of preparation are filled into PVC and (mass ratio=1 of calcium sulfate crystal whiskers and PVC: 10), are gone forward side by side
Row plastics bending property is tested, and the results are shown in Table 2, the results showed that it is straight that plastic plate and PVC made of calcium sulfate crystal whiskers is added in PVC
It connects manufactured plastic plate (table 1) to compare, the bending modulus of material improves 10.7%.
Embodiment 2：
The lignin suspension for taking 2L paper industries to generate carries out vacuum filter using the polypropylene fibre filter cloth of 300 mesh, obtains wood
Quality black liquor.The black liquor of acquisition is subjected to ultrasound 20min, 30wt%H is pumped into dropwise using peristaltic pump2SO4, keep stirring in the process
It mixes, room temperature, adjusts pH to 1.5, lignin is made to settle, and pH is kept to continue to stir 2h not higher than 1.5；Then using hypervelocity
Centrifuge is separated by solid-liquid separation at 12000rpm, time 15min, is obtained the supernatant fluid containing more sulfate ion and (is surveyed
It is 45g/L to obtain sulfate radical content), it is slowly added to a small amount of calcium oxide solid powder, process holding is sufficiently stirred, and waits for that pH stablizes
Afterwards, lime powder is continuously added, until pH stablizes between 5.5~7.0, continues to stir 1h, it is made fully to react.Then plus
Enter the citric acid that mass fraction is 0.3%, after being sufficiently stirred, slurries are directly transferred in stainless steel autoclave, is arranged
At 160 DEG C, process is kept stirring temperature in autoclave, reacts 5h, and lower tank (is measured by filtering to be separated by solid-liquid separation
Sulfate ion concentration is 1.3g/L in supernatant, 97%) removal rate of sulfate ion reaches, and hot water is used in combination to wash solid,
And be placed in 80 DEG C of baking ovens and be dried, after 3h, solid is transferred in 850 DEG C of high temperature furnace and carries out calcining 3h, then dropped
Calcium sulfate crystal whiskers are obtained to room temperature, it is 0.22g/ml, whiteness 88, draw ratio 1: 50~90, heat analysis to measure its bulk density
The result shows that its water content is 0.
The 10g calcium sulfate crystal whiskers of preparation are filled into PVC and (mass ratio=1 of calcium sulfate crystal whiskers and PVC: 10), are gone forward side by side
Row plastics bending property is tested, and the results are shown in Table 3, the results showed that it is straight that plastic plate and PVC made of calcium sulfate crystal whiskers is added in PVC
It connects manufactured plastics (table 1) to compare, the bending modulus of material improves 13.9%.
Embodiment 3
The lignin suspension for taking 2L paper industries to generate carries out vacuum filter using the polypropylene fibre filter cloth of 300 mesh, obtains wood
Quality black liquor.The black liquor of acquisition is subjected to ultrasound 20min, 50wt%H is pumped into dropwise using peristaltic pump2SO4, keep stirring in the process
It mixes, adjusts pH to 1.0, lignin is made to settle, and pH is kept to continue to stir 1h not higher than 1.0；Then existed using ultracentrifuge
It is separated by solid-liquid separation under 14000rpm, time 20min, obtains the supernatant fluid containing more sulfate ion and (measure sulfate radical
Content is 55g/L), it is slowly added to a small amount of calcium hydroxide solid powder, process holding is sufficiently stirred, and after pH stabilizations, is continued
Calcium hydroxide powder is added, until pH stablizes between 5.5~7.0, continues to stir 2h, it is made fully to react.Matter is then added
The malic acid that score is 0.5% is measured, after being sufficiently stirred, slurries are directly transferred in stainless steel autoclave, high pressure is set
At 170 DEG C, process is kept stirring temperature in reaction kettle, reacts 6h, and lower tank (measures supernatant by filtering to be separated by solid-liquid separation
Sulfate ion concentration is 1.4g/L in liquid, and 97.5%) removal rate of sulfate ion reaches, and solid is washed with water, then
It is placed in 80 DEG C of baking ovens and is dried, after 3h, solid is transferred in 950 DEG C of high temperature furnace and carries out calcining 4h, is then down to room
Temperature obtains calcium sulfate crystal whiskers, and it is 0.21g/ml, whiteness 89, draw ratio 1: 30~60, heat analysis result to measure its bulk density
Show that its water content is 0.
The calcium sulfate crystal whiskers of preparation are filled into PVC and (mass ratio=1 of calcium sulfate crystal whiskers and PVC: 10), and are moulded
Expect bending property experiment, the results are shown in Table 4, the results showed that PVC is added plastic plate and PVC made of calcium sulfate crystal whiskers and directly makes
At plastics (table 1) compare, the bending modulus of material improves 11.0%.
Table 1
Table 2
Table 3
Table 4
Claims (8)
1. a kind of method that sulfate radical using in sour dead-wood quality black liquor prepares calcium sulfate crystal whiskers, which is characterized in that including with
Lower step：
(1) lignin suspension is filtered, obtains lignin black liquor, sulfuric acid is instilled into the lignin black liquor, adjusted
PH to 1.0~3.0；
(2) system that step (1) obtains is separated by solid-liquid separation, take gained liquid, into the liquid be added calcium hydroxide or
Calcium oxide obtains precipitated liquid system；
(3) organic acid is added into the precipitated liquid system, then carries out hydro-thermal process, the temperature of hydro-thermal process is 150~170
DEG C, the time of hydro-thermal process is 4~6h, obtains calcium sulfate crystal whiskers suspension；
(4) the calcium sulfate crystal whiskers suspension is separated by solid-liquid separation, dried, calcined, obtain calcium sulfate crystal whiskers.
2. according to the method described in claim 1, it is characterized in that, in step (1), the lignin suspension is paper industry
Or the lignin suspension that stalk corn processing industry generates, main component have lignin, cellulose and hemicellulose, wherein
Content of lignin is 18~25g/L.
3. described to be filtered into using 300 mesh or more according to the method described in claim 1, it is characterized in that, in step (1)
Nylon-type filter cloth is filtered lignin suspension.
4. according to the method described in claim 1, it is characterized in that, in step (1), first the lignin black liquor is surpassed
Sound, stirring, then sulfuric acid is instilled thereto.
5. according to the method described in claim 1, it is characterized in that, in step (1), the sulfuric acid used a concentration of 5~
50wt%.
6. according to the method described in claim 1, it is characterized in that, in step (2), calcium hydroxide or calcium oxide is added until molten
The pH of liquid is 5.5~7.0.
7. according to the method described in claim 1, it is characterized in that, in step (3), the organic acid be citric acid, lactic acid or
Malic acid, the addition of the organic acid are the 0.1~0.5% of precipitated liquid system gross mass.
8. according to the method described in claim 1, it is characterized in that, in step (3), drying temperature is 60~120 DEG C, when drying
Between 2~4h, calcination temperature be 750~950 DEG C, calcination time be 3~4h.
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| CN102352535A (en) * | 2011-09-22 | 2012-02-15 | 东莞上海大学纳米技术研究院 | Method for preparing calcium sulfate crystal whiskers from desulfurized gypsum under normal pressure |
| CN102583688A (en) * | 2012-02-27 | 2012-07-18 | 长沙理工大学 | Method for treating and reusing pulping black liquor acidification lignin wastewater |
| CN103014831A (en) * | 2012-12-28 | 2013-04-03 | 殷义甫 | Production method of ultrapure calcium sulfate whiskers |
| CN103540996A (en) * | 2013-09-27 | 2014-01-29 | 蚌埠丰原医药科技发展有限公司 | Method for producing calcium sulfate whiskers from waste sulfuric acid |
| CN103966670A (en) * | 2014-05-12 | 2014-08-06 | 江苏一夫科技股份有限公司 | Method for integrating waste sulfuric acid treatment engineering and gypsum crystal whisker production |
| US20150158997A1 (en) * | 2013-12-06 | 2015-06-11 | Georgia-Pacific Gypsum Llc | Gypsum composite modifiers |
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| CN102352535A (en) * | 2011-09-22 | 2012-02-15 | 东莞上海大学纳米技术研究院 | Method for preparing calcium sulfate crystal whiskers from desulfurized gypsum under normal pressure |
| CN102583688A (en) * | 2012-02-27 | 2012-07-18 | 长沙理工大学 | Method for treating and reusing pulping black liquor acidification lignin wastewater |
| CN103014831A (en) * | 2012-12-28 | 2013-04-03 | 殷义甫 | Production method of ultrapure calcium sulfate whiskers |
| CN103540996A (en) * | 2013-09-27 | 2014-01-29 | 蚌埠丰原医药科技发展有限公司 | Method for producing calcium sulfate whiskers from waste sulfuric acid |
| US20150158997A1 (en) * | 2013-12-06 | 2015-06-11 | Georgia-Pacific Gypsum Llc | Gypsum composite modifiers |
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