CN1718543A - Preparation method of polyaluminum chloride with high aluminum content - Google Patents
Preparation method of polyaluminum chloride with high aluminum content Download PDFInfo
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- CN1718543A CN1718543A CN 200410068837 CN200410068837A CN1718543A CN 1718543 A CN1718543 A CN 1718543A CN 200410068837 CN200410068837 CN 200410068837 CN 200410068837 A CN200410068837 A CN 200410068837A CN 1718543 A CN1718543 A CN 1718543A
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- Prior art keywords
- aluminum chloride
- catalyst
- polymerize aluminum
- aluminium hydroxide
- aluminium
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Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 37
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title abstract 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 56
- 238000006243 chemical reaction Methods 0.000 claims abstract description 45
- 239000003054 catalyst Substances 0.000 claims abstract description 44
- 239000004411 aluminium Substances 0.000 claims abstract description 34
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 31
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims abstract description 30
- 238000000034 method Methods 0.000 claims abstract description 30
- 239000002994 raw material Substances 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims abstract description 6
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 4
- 239000011574 phosphorus Substances 0.000 claims abstract description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 162
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 14
- 230000032683 aging Effects 0.000 claims description 13
- 238000006116 polymerization reaction Methods 0.000 claims description 11
- 238000013019 agitation Methods 0.000 claims description 7
- 235000011007 phosphoric acid Nutrition 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 5
- -1 phosphorus compound Chemical class 0.000 claims description 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229940045641 monobasic sodium phosphate Drugs 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims description 3
- 239000004254 Ammonium phosphate Substances 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 2
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 2
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 2
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 claims description 2
- 235000019800 disodium phosphate Nutrition 0.000 claims description 2
- 230000029087 digestion Effects 0.000 claims 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 17
- 239000000047 product Substances 0.000 abstract description 14
- 239000006228 supernatant Substances 0.000 abstract description 12
- 239000010865 sewage Substances 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 238000010438 heat treatment Methods 0.000 abstract description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 abstract 2
- 238000000151 deposition Methods 0.000 abstract 2
- 239000012535 impurity Substances 0.000 abstract 1
- 239000012629 purifying agent Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 22
- 238000004062 sedimentation Methods 0.000 description 17
- 239000007788 liquid Substances 0.000 description 14
- 239000011541 reaction mixture Substances 0.000 description 9
- 239000013049 sediment Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- XFBXDGLHUSUNMG-UHFFFAOYSA-N alumane;hydrate Chemical compound O.[AlH3] XFBXDGLHUSUNMG-UHFFFAOYSA-N 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 239000012153 distilled water Substances 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 5
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 description 3
- 239000000701 coagulant Substances 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910001388 sodium aluminate Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229940037003 alum Drugs 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 229920002521 macromolecule Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000001164 aluminium sulphate Substances 0.000 description 1
- 235000011128 aluminium sulphate Nutrition 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000011089 carbon dioxide Nutrition 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- BUACSMWVFUNQET-UHFFFAOYSA-H dialuminum;trisulfate;hydrate Chemical compound O.[Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O BUACSMWVFUNQET-UHFFFAOYSA-H 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 150000003016 phosphoric acids Chemical class 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
Abstract
The invention relates to a preparation method of polyaluminium chloride with high aluminium content, in particular to a method for directly preparing the polyaluminium chloride with high purity and high aluminium content by using aluminium hydroxide as a raw material through a one-step method, wherein the aluminium hydroxide and industrial hydrochloric acid are uniformly mixed in a reaction kettle, a phosphorus-containing compound catalyst is added or the phosphorus-containing compound catalyst and the aluminium-containing compound catalyst are simultaneously added, and the steam pressure is 1-8.0 Kgf/cm2Heating to 90-180 deg.C, reacting for more than 2 hr, and depositing in a depositing tank to obtain the supernatant as polyaluminium chloride product, which has amorphous structure, low impurity content, high aluminum content increased by 30% or more, high material utilization rate and no pollution. Compared with the prior art, the product can improve the water purifying effect of industrial sewage by about 30 percent as an industrial sewage purifying agent.
Description
Technical field
The present invention relates to polymerize aluminum chloride, relate in particular to the preparation method of the polymerize aluminum chloride of high aluminium content.
Background technology
At present, polymerize aluminum chloride claims aluminium chlorohydroxide or aluminium chlorohydroxide again, is the middle macromolecular compound between six water aluminum chlorides and aluminium hydroxide, and its chemical general formula is [Al
2(OH)
nCl
6-n]
m, wherein m is smaller or equal to 10, and n equals 1 to 5.Because polymerize aluminum chloride is the macromolecular compound of building bridge and to be polymerized by hydroxyl, so very easily water-soluble and hydrolysis can take place and produce a series of physics chemical action such as cohesion, absorption, precipitation.Therefore, polymerize aluminum chloride is often used as water conditioner, to remove the foreign material in anhydrating.But because the polymerize aluminum chloride concentration of preparation is low, drying condition is difficult, so usually all with the liquid product supply, usage quantity is bigger again, trucking costs is also high, thereby it is used restriction to some extent.
In the prior art, be the method that raw material is produced polymerize aluminum chloride, gel method, sour molten two step method, acid-soluble one-step are arranged with hydrochloric acid and aluminium hydroxide.Its reaction formula is:
Gel method: under normal pressure, crystalline aluminium hydroxide solubleness in hydrochloric acid is less, the equivalence ratio of aluminium is less than 1.0 in the common dissolution fluid, must at first crystalline aluminium hydroxide be become amorphous gel, mainly generate sodium aluminate by crystalline aluminium hydroxide and sodium hydroxide reaction, in sodium aluminate, feed carbonic acid gas, make it become gluey aluminium hydroxide, gluey aluminium hydroxide again with hydrochloric acid reaction get final product the polymerize aluminum chloride product.The key of this technology is that carbonating is decomposed; Advantage is the working condition gentleness, good product quality; Shortcoming is a long flow path, and production cost is higher.The molten two step method of hydroxide aluminic acid is: the molten process of two hypo acids is arranged, industrial aluminium hydroxide generates alum liquor with sulfuric acid dissolution, the reaction that is hydrolyzed in certain proportion of alum liquor and ammoniacal liquor, prepare active basic aluminium sulphate gel, after reaction finishes, slip is sent into the pressure filter press filtration, and filtrate (ammonium sulfate) is reclaimed, and filter cake carries out polyreaction at normal temperatures with hydrochloric acid again can make the liquid aluminium polychloride finished product.This technology is domestic and international most important industrialized preparing process, and technology is simple, ripe, and the constant product quality performance is good, and cost is low, and the aluminium solubility rate can reach 70-95%.Aluminium hydroxide acid-soluble one-step: CN.1069006 discloses a kind of sour molten technology of a step, 20% hydrochloric acid and aluminium hydroxide were added reactor by weight 5.8: 1, add 5.8% sulfuric acid simultaneously and make solubility promoter, stir, be warming up to 80-90 ℃, keep system pressure about 0.2MPa, 2.5 hours reaction times, most of solid aluminum hydroxide dissolving this moment, with ammoniacal liquor regulation system pH to 3.5 yellow transparent liquid, through the cooling, filter product.This production technique is simple, and facility investment is little, and is with short production cycle, and good quality of product is a kind of production technique that is worthy to be popularized.CN1046512A also discloses an another kind of step acid pasting technology, major technique is: mix under in reactor industrial goods aluminium hydrate powder and technical hydrochloric acid being stirred, add catalyzer (low polymerization degree polymerize aluminum chloride), use steam heating, reacted 6-8 hour, in settling bath, precipitate then,, directly make product again in the drying machine drying.This technology is simple, and product contains heavy metal ion few (not fluorine-containing and mercury), the product stability height, and basicity can reach 45-50%.
In sum, three kinds of methods that aluminium hydroxide and hydrochloric acid reaction prepare polymerize aluminum chloride respectively have relative merits, and its common issue with is that Production Flow Chart is long and complicated, make output be subjected to certain restriction, thereby cost is higher.Especially the aluminium content in the polymerize aluminum chloride is low, just is difficult to flow when aluminium content is high in the liquid; The x diffraction is indicated as crystal state after forming solid, and dispersing property is poor.
Summary of the invention
The purpose of this invention is to provide a kind of low cost of manufacture, foreign matter content is not high, basicity is greater than the preparation method of 40% polymerize aluminum chloride, the polymerize aluminum chloride that Using such method makes has aluminium content height and solid form is the characteristic of amorphous structure, being used for industrial sewage handles, than the polymerize aluminum chloride that uses prior art to obtain, purifying water effect can improve about 30%.
For achieving the above object, the technical solution used in the present invention is:
With raw material is the crystalline aluminium hydroxide and the hydrochloric acid reaction of industrial goods, and the molar ratio of aluminium hydroxide and hydrochloric acid is 0.4-1: 2, be preferably 0.6-0.8: 1.In reactor, add the hydrochloric acid soln for preparing earlier, under the agitation condition, and then add aluminium hydrate powder slowly, under the condition that stirs, add catalyst A, the add-on of catalyst A is: the ratio of aluminium hydroxide and A is 2-50 (mol ratio), is preferably 3-12 (mol ratio), is 1-8Kgf/cm at vapor pressure
2Condition under, it is heated to 90-180 ℃, preferably temperature is at 110-150 ℃, the reaction times, the reaction times was preferably 4-5 hour more than 2 hours, after reaction finished, the polymeric aluminium reaction thing of generation was put into settling bath, ageing is more than 2 hours.Clear liquid is the polymerize aluminum chloride finished product above after the ageing, shows that by analysis this polymerize aluminum chloride has aluminium content height, structure is unbodied feature.Among the present invention, catalyst A is an inorganic phosphorus compound, particularly phosphoric acid, phosphoric acid salt such as ortho-phosphoric acid, phosphorous acid, ammonium phosphate, primary ammonium phosphate, Secondary ammonium phosphate, aluminum phosphate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, tetra-sodium can be one or more mixtures wherein.The adding mode of defined catalyst A not among the present invention can add simultaneously also and can add after reaction for some time with hydrochloric acid.
Raw material of the present invention is preferably purity than higher industrial goods, and the alumina content of aluminium hydroxide is more preferably greater than 63% (mass ratio), and the pure hydrogen cloride concentration of technical hydrochloric acid is preferably 15-37% (mass ratio).
It is to analyze from structure after the catalyst A that the contriver finds to add P contained compound, and the form of polymerize aluminum chloride tends to amorphous variation, and dispersing property is good.Do not add catalyst A, the polymerize aluminum chloride of preparation shows as crystalline state, and dispersing property is poor.Along with the increase of catalyst A add-on, the aluminum content height of the polymerize aluminum chloride that obtains, density is big, and the basicity height illustrates that catalyst A can improve the aluminium content of polymerize aluminum chloride, can improve the basicity of polymerize aluminum chloride simultaneously.
The contriver also finds, when adding catalyst A, adds catalyst B again, and the gained polymerize aluminum chloride has more superperformance: form is amorphous, good dispersity, aluminium amount height, basicity height.Be not specially limited the add-on of catalyst B among the present invention, the aluminium hydroxide of recommending among the present invention and the ratio of catalyst B are 0.5-6 (mass ratioes), and preferably ratio is 1-3 (mass ratio), reacts according to identical reaction conditions and produces polymerize aluminum chloride.The polymerize aluminum chloride of gained shows by analysis thus, and the polymerization degree is more than 40%, and aluminium content has obtained further raising, and structure is amorphous.Catalyst B is aluminiferous compound, as the polymerize aluminum chloride of low polymerization degree, aluminum chloride, aluminate etc., can be one or more mixture wherein.The polymerize aluminum chloride of low polymerization degree is meant that basicity is lower than 25% polymerize aluminum chloride.
Characteristics of the present invention are:
(1). the metallic aluminium content height of finished product polymerize aluminum chloride, higher 1.5 more than the unit than prior art, foreign matter content is low;
(2). prepared polymerize aluminum chloride is amorphous through using the X-ray diffraction to be determined as after the oven dry;
(3). prepared polymerize aluminum chloride is 8% (mass ratio) when above at metallic aluminium content, and is mobile fine, the phenomenon of condensing can not occur, and the polymerize aluminum chloride of prior art for preparing the phenomenon of condensing just occurs easily when metallic aluminium content is 7.5%.
(4). prepared polymerize aluminum chloride is scattered in the industrial sewage easily, and when this polymerize aluminum chloride joined in the industrial sewage, the alumen ustum of formation was big, and purifying water effect is good.
(5). preparation technology is simple, and reaction time is short, and is pollution-free.
The polymerize aluminum chloride structure of using method of the present invention to produce has amorphous feature, and foreign matter content is low, and aluminium content can improve more than 30%, and the raw material availability height is pollution-free.This product compared with prior art, can improve industrial sewage purifying water effect about 30% as the industrial sewage water purification agent.
Description of drawings
Fig. 1 is the XRD figure of different preparation method's gained polymerize aluminum chlorides, wherein a: Comparative Examples 1 is the 0# sample, and b, c, d, e, f are embodiment 1,2,3,4,5 gained polymerize aluminum chlorides, are specially the b:1# sample; The c:2# sample; The d:3# sample; The e:4# sample; The f:5# sample.
As can be seen from Figure 1, Comparative Examples 1 does not add catalyst A, and the polymerize aluminum chloride of preparation shows as crystalline state, and embodiment adds catalyst A, and the polymerize aluminum chloride of preparation shows as amorphous state.
Fig. 2 is the XRD figure of Comparative Examples 1, embodiment 6 gained polymerize aluminum chloride performances, and as can be seen from Figure 2, the polymerize aluminum chloride (6# sample) that embodiment 6 adds catalyst A, B preparation simultaneously shows as amorphous state.
Fig. 3 is the XRD figure of embodiment 7,8 gained polymerize aluminum chloride performances, as can be seen from Figure 3, requires the polymerize aluminum chloride (7#, 8# sample) of preparation to show as amorphous state according to invention.
Fig. 4 is the XRD figure of Comparative Examples 1, Comparative Examples 2 gained polymerize aluminum chloride performances, and as can be seen from Figure 4, Comparative Examples 2 does not add catalyst A, only adds catalyst B, and the polymerize aluminum chloride sample of preparation (9# sample) is measured and is indicated as crystalline state.
Embodiment
In order further to set forth characteristics of the present invention, below with the specific embodiment explanation.But these examples can not limit the present invention.
(1) the main analytical procedure of the present invention
1. the mensuration of the aluminium in the polymerize aluminum chloride: undertaken by GB15892-95;
2. the polymerize aluminum chloride basicity is analyzed: undertaken by GB15892-95;
3. the material phase analysis of polymerize aluminum chloride: X-ray diffraction method, ASTM D3942.
(2) raw materials used specification in the example of the present invention
1. aluminium hydroxide: industrial goods, alumina content are more than 63% (mass percent), are undertaken by the GB/T6610-86 standard;
2. hydrochloric acid: analytical pure or industrial goods, concentration are 15-37% (mass ratio), are undertaken by the GB320-93 standard;
3. distilled water or be deionized water.
Embodiment 1
In the acid-resistant reacting kettle of 250mL, the distilled water of measuring 64mL adds wherein, and then the concentration that adds 120mL is 36% (mass ratio), density is that the concentrated hydrochloric acid of 1.19g/mL is in reactor, agitation condition slowly adds the 90g aluminium hydrate powder of metering down, after adding the ortho-phosphoric acid catalyst A of 4g, under 1.5Kgf/cm2 pressure, carry out chemical reaction, when temperature of reaction is 110 ℃, when keeping thermometer 4 hours, the taking-up reaction mixture is put into settling bath and was carried out ageing 16 hours, and the lower sediment thing returns reactor and continues reaction, and supernatant liquid is polymerize aluminum chloride sample 1#, experimental result sees Table 1, and its structure is seen Fig. 1.
Embodiment 2
Adopt the condition of embodiment 1, phosphorous acid catalyst A and the concentrated hydrochloric acid of different is 12g add simultaneously, at 2Kgf/cm
2Carry out chemical reaction under the pressure, when temperature of reaction is 110 ℃, when keeping thermometer 5 hours, the taking-up reaction mixture is put into settling bath and was carried out ageing 20 hours, the lower sediment thing returns reactor and continues reaction, supernatant liquid is polymerize aluminum chloride sample 2#, and experimental result sees Table 1, and its structure is seen Fig. 1.
Embodiment 3
Adopt the condition of embodiment 1, different is that concentrated hydrochloric acid and aluminium hydroxide reacted after 0.5 hour, adds the primary ammonium phosphate catalyst A of 16g again, at 3Kgf/cm
2Continue reaction under the pressure, when temperature of reaction is 120 ℃, when keeping thermometer 6 hours, the taking-up reaction mixture is put into settling bath and was carried out ageing 48 hours, the lower sediment thing returns reactor and continues reaction, supernatant liquid is polymerize aluminum chloride sample 3#, and experimental result sees Table 1, and its structure is seen Fig. 1.
Embodiment 4
Adopt the condition of embodiment 1, different is after adding the SODIUM PHOSPHATE, MONOBASIC catalyst A of 28g, at 1Kgf/cm
2Carry out chemical reaction under the pressure, when temperature of reaction is 130 ℃, when keeping thermometer 3 hours, the taking-up reaction mixture is put into settling bath and was carried out ageing 10 hours, the lower sediment thing returns reactor and continues reaction, supernatant liquid is polymerize aluminum chloride sample 4#, and experimental result sees Table 1, and its structure is seen Fig. 1.
Embodiment 5
Adopt the condition of embodiment 1, different is after adding the tetra-sodium catalyst A of 38g, at 1.2Kgf/cm
2Carry out chemical reaction under the pressure, when temperature of reaction is 135 ℃, when keeping thermometer 8 hours, the taking-up reaction mixture is put into settling bath and was carried out ageing 32 hours, the lower sediment thing returns reactor and continues reaction, supernatant liquid is polymerize aluminum chloride sample 5#, and experimental result sees Table 1, and its structure is seen Fig. 1.
Comparative Examples 1
Adopt the condition of embodiment 1, different is not add catalyst A.With the liquid aluminium polychloride sample of gained is 0#, and its experiment the results are shown in Table 1, and structure is seen Fig. 1.
As can be seen from Figure 1, Comparative Examples 1 does not add catalyst A, and the polymerize aluminum chloride of preparation shows as crystalline state, and basicity is the polymerize aluminum chloride of low polymerization degree less than 25%.Embodiment adds catalyst A, and the polymerize aluminum chloride of preparation shows as amorphous state, and aluminium content, basicity all are improved in the polymerize aluminum chloride.
The physical data contrast of table 1 embodiment 1-5 and Comparative Examples 1 gained polymerize aluminum chloride
| Sample number into spectrum | Aluminium content, m% | Basicity, % | Density, g/cm 3 | |
| Embodiment | 1# | 7.04 | 33 | 1.300 |
| 2# | 7.49 | 37 | 1.320 | |
| 3# | 7.59 | 40 | 1.372 | |
| 4# | 8.08 | 47 | 1.400 | |
| 5# | 9.54 | 55 | 1.560 | |
| Comparative Examples | 0# | 6.03 | 22 | 1.210 |
Embodiment 6
In order further to improve the aluminium content in the polymerize aluminum chloride, carried out again in the acid-resistant reacting kettle of 500mL, the distilled water of measuring 138mL adds wherein, and then the concentration that adds 300mL is that 36% (mass ratio), density are that the concentrated hydrochloric acid of 1.19g/mL is in reactor, agitation condition slowly adds the 220g aluminium hydrate powder of metering down, after adding ortho-phosphoric acid 30g catalyst A and Comparative Examples 1 gained low polymerization degree polymerize aluminum chloride (0# sample) 60g catalyst B simultaneously, at 2Kgf/cm
2Carry out chemical reaction under the pressure, when temperature of reaction is 140 ℃, when keeping thermometer 3 hours, the taking-up reaction mixture is put into settling bath and was carried out ageing 12 hours, the lower sediment thing returns reactor and continues reaction, supernatant liquid is polymerize aluminum chloride sample 6#, and experimental result sees Table 2, and its structure is seen Fig. 2.
Table 2 embodiment 6 contrasts with the rerum natura of Comparative Examples 1 gained polymerize aluminum chloride
| Numbering/sample number | Aluminium content, m% | Basicity, % | Density, g/cm 3 | |
| Embodiment 6 | 6# | 9.50 | 45 | 1.470 |
| Comparative Examples 1 | 0# | 6.03 | 22 | 1.210 |
From table 2 and Fig. 2 as can be seen, in embodiment 6, add catalyst A and B simultaneously after, structure is unbodied feature, and the high feature of aluminium content is arranged.
Embodiment 7
In the acid-resistant reacting kettle of 500mL, the distilled water of measuring 100mL adds wherein, and then the concentration that adds 125mL is 30% (mass ratio), density is that the technical hydrochloric acid of 1.149g/mL is in reactor, agitation condition slowly adds the 185g aluminium hydrate powder of metering down, (wherein ortho-phosphoric acid is 1.9g to the catalyst A of adding 7.6g, tetra-sodium is 5.7g) after, under 1.5Kgf/cm2 pressure, carry out chemical reaction, when temperature of reaction is 120 ℃, when keeping thermometer 3 hours, the taking-up reaction mixture is put into settling bath and was carried out ageing 5 hours, the lower sediment thing returns reactor and continues reaction, supernatant liquid is polymerize aluminum chloride sample 7#, and experimental result sees Table 3, and its structure is seen Fig. 3.
Embodiment 8
In the acid-resistant reacting kettle of 2000mL, the distilled water of measuring 368mL adds wherein, and then the concentration that adds 1382mL is that 32% (mass ratio), density are that the technical hydrochloric acid of 1.159g/mL is in reactor, agitation condition slowly adds the 826g aluminium hydrate powder of metering down, add catalyst A simultaneously and be 118g (ortho-phosphoric acid) and catalyst B and be 238g (Comparative Examples 1 gained low polymerization degree polymerize aluminum chloride 0# sample 204g wherein, sodium aluminate is 34g) after, at 2Kgf/cm
2Carry out chemical reaction under the pressure, when temperature of reaction is 135 ℃, when keeping thermometer 5 hours, the taking-up reaction mixture is put into settling bath and was carried out ageing 8 hours, the lower sediment thing returns reactor and continues reaction, supernatant liquid is polymerize aluminum chloride sample 8#, and experimental result sees Table 3, and its structure is seen Fig. 3.
The rerum natura contrast of table 3 embodiment 7-8 and Comparative Examples 1 gained polymerize aluminum chloride
| Numbering/sample number | Aluminium content, m% | Basicity, % | Density, g/cm 2 | |
| Embodiment 7 | 7# | 8.92 | 45 | 1.475 |
| Embodiment 8 | 8# | 10.12 | 53 | 1.485 |
| Comparative Examples 1 | 0# | 6.03 | 22 | 1.210 |
From table 3 and Fig. 3 as can be seen, use the polymerize aluminum chloride of gained of the present invention, the alumina content height, structure is the indefiniteness attitude.
Comparative Examples 2
According to the method among the patent CN1046512A, in the acid-resistant reacting kettle of 500mL, the distilled water of measuring 128mL adds wherein, and then the concentration that adds 250mL is that 36% (mass ratio), density are that the concentrated hydrochloric acid of 1.19g/mL is in reactor, agitation condition slowly adds the 200g aluminium hydrate powder of metering down, after adding 50g Comparative Examples 1 gained low polymerization degree polymerize aluminum chloride (0# sample) again, at 2Kgf/cm
2Carry out chemical reaction under the pressure, when temperature of reaction is 120 ℃, when keeping thermometer 8 hours, the taking-up reaction mixture is put into settling bath and was carried out ageing 72 hours, the lower sediment thing returns reactor and continues reaction, supernatant liquid is polymerize aluminum chloride sample 9#, and experimental result sees Table 4, and its structure is seen Fig. 4.
The rerum natura of table 4 Comparative Examples 2 gained polymerize aluminum chlorides
| Sample number | Aluminium content, m% | Basicity, % | Density, g/cm 2 |
| 9# | 8.14 | 33 | 1.370 |
| 0# | 6.03 | 22 | 1.210 |
From table 4 and Fig. 4 as can be seen, add the polymerize aluminum chloride of low polymerization degree after, aluminium content and basicity in the polymerize aluminum chloride all have corresponding raising, but can find out still that from form it is a crystal habit.
Comprehensive above embodiment, Comparative Examples according to the polymerize aluminum chloride of the inventive method preparation, are compared with Comparative Examples as can be seen, and maximum characteristics are alumina content height, and structure is an amorphous state, shows that dispersing property is good, indicates that its water treatment is effective.
Application experiment as water conditioner
For high aluminium content polymerize aluminum chloride newly developed application experiment as water conditioner is described, carry out application test with representational sample.Testing sequence is: 0# sample, 4# sample and the 6# sample of getting metering, join respectively in the industrial condensed oil sewage of 100mL, stir 2min fast, middling speed stirs 4min, stir 8min at a slow speed, standing sedimentation 50min utilizes turbidimeter to measure the turbidity of supernatant liquor, with acidity instrumentation supernatant liquor pH value, the The apparent phenomenon in the while viewing test process.It the results are shown in Table 5,6,7.
Table 5 Comparative Examples 1 gained 0# sample optimal coagulant dose test-results
| Volume (mL) | Dosage (mg/L) | Surplus turbid (NTU) | The pH value | The apparent phenomenon |
| 100 | 490 | 12.0 | 6.60 | Flco is big, and volume is little, and sedimentation is slow, and is colourless |
| 100 | 570 | 11.5 | 6.81 | Flco is big, and volume is little, and sedimentation is fast, and is colourless |
| 100 | 650 | 13.5 | 6.72 | Flco is big, and volume is big, and layering is slow, |
| 100 | 730 | 22.3 | 6.83 | Flco is little, and volume is big, and layering is slow, |
| 100 | 810 | 25.1 | 6.75 | Flco is little, and volume is big, and layering is slow, |
Table 6 embodiment 4 gained 4# sample optimal coagulant dose test-results
| Volume (mL) | Dosage (mg/L) | Surplus turbid (NTU) | The pH value | The apparent phenomenon |
| 100 | 253 | 18.1 | 5.76 | Flco is big, and volume is little, and sedimentation is slow, and is colourless |
| 100 | 295 | 14.6 | 5.51 | Flco is big, and volume is little, and sedimentation is fast, and is colourless |
| 100 | 338 | 11.8 | 3.95 | Flco is big, and volume is big, and sedimentation is fast, and is colourless |
| 100 | 380 | 16.5 | 3.81 | Flco is big, and volume is big, and sedimentation is fast, and is colourless |
| 100 | 420 | 15.6 | 3.51 | Flco is big, and volume is big, and sedimentation is fast, and is colourless |
Table 7 embodiment 6 gained 6# sample optimal coagulant dose test-results
| Volume (mL) | Dosage (mg/L) | Surplus turbid (NTU) | The pH value | The apparent phenomenon |
| 100 | 220 | 2.6 | 6.81 | Flco is big, and volume is little, and sedimentation is fast, and is colourless |
| 100 | 260 | 2.7 | 6.62 | Flco is big, and volume is big, and sedimentation is fast, and is colourless |
| 100 | 300 | 1.6 | 6.65 | Flco is big, and volume is big, and sedimentation is fast, and is colourless |
| 100 | 320 | 2.5 | 6.86 | Flco is big, and volume is big, and sedimentation is fast, and is colourless |
| 100 | 380 | 2.3 | 6.91 | Flco is big, and volume is big, and sedimentation is fast, and is colourless |
| 100 | 420 | 5.6 | 6.75 | Flco is big, and volume is big, and sedimentation is fast, and is colourless |
| 100 | 460 | 6.2 | 6.82 | Flco is big, and volume is big, and sedimentation is fast, and is colourless |
| 100 | 510 | 7.8 | 6.78 | Flco is big, and volume is big, and sedimentation is fast, and is colourless |
From table 5, table 6 and table 7 result as can be seen, the high aluminium content polymerize aluminum chloride of using the embodiments of the invention gained is used for industrial sewage to be handled, and advantages such as consumption is few, flco is big, sedimentation is fast, stable performance, good decolorizing effect are arranged.
Claims (12)
1. the preparation method of a high aluminium content polymerize aluminum chloride, raw material is aluminium hydroxide and hydrochloric acid, it is characterized in that: in reactor, add hydrochloric acid soln earlier, under the agitation condition, add the crystalline aluminium hydroxide of industrial goods, the molar ratio of aluminium hydroxide and hydrochloric acid is 0.4-1: 2, and have catalyst A to participate in reaction process, the mol ratio of aluminium hydroxide and A is 2-50, is 1-8Kgf/cm at vapor pressure
2Condition under, temperature of reaction is 90-180 ℃, the reaction times is more than 2 hours, after reaction finished, the polymeric aluminium reaction thing of generation was put into settling bath, ageing is more than 2 hours, and the top stillness of night is the polymerize aluminum chloride finished product after the ageing, and this polymerize aluminum chloride structure has amorphous feature; Catalyst A is an inorganic phosphorus compound.
2. method according to claim 1 is characterized in that catalyst B is aluminiferous compound except that there being catalyst A to participate in also having added another kind of catalyst B the reaction process.
3. according to claim 1 or 4 described methods, the molar ratio that it is characterized in that aluminium hydroxide and hydrochloric acid is 0.6～0.8: 1.
4. according to claim 1 or 4 described methods, it is characterized in that the add-on of catalyst A is: the mol ratio of aluminium hydroxide and A is 3-12.
5. according to claim 1 or 4 described methods, it is characterized in that aluminium hydroxide and hydrochloric acid are industrial goods, the aluminum oxide quality content of aluminium hydroxide is greater than 63%, and the pure hydrogenchloride mass concentration of technical hydrochloric acid is 15～37%.
6. according to claim 1 or 4 described methods, it is characterized in that temperature of reaction is 110～150 ℃.
7. according to claim 1 or 4 described methods, it is characterized in that the reaction times is 4～5 hours.
8. according to claim 1 or 4 described methods, it is characterized in that digestion time is 24～48 hours.
9. according to claim 1 or 4 described methods, it is characterized in that catalyst A is ortho-phosphoric acid, phosphorous acid, ammonium phosphate, primary ammonium phosphate, Secondary ammonium phosphate, aluminum phosphate, SODIUM PHOSPHATE, MONOBASIC, Sodium phosphate dibasic, tetra-sodium, can be one or more mixture wherein.
10. method according to claim 4, it is characterized in that catalyst B is polymerize aluminum chloride, aluminum chloride, the aluminate of low polymerization degree, can be one or more mixture wherein, the polymerize aluminum chloride of low polymerization degree be meant that basicity is lower than 25% polymerize aluminum chloride.
11. according to claim 4 or 12 described methods, the mass ratio that it is characterized in that aluminium hydroxide and catalyst B is 0.5～6.
12. according to claim 4 or 12 described methods, the mass ratio that it is characterized in that aluminium hydroxide and catalyst B is 1～3.
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| CN101306827B (en) * | 2008-06-11 | 2010-07-28 | 中国石油天然气股份有限公司 | Method for preparing polyaluminium chloride by firing waste residues with sludge |
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| JPS6114126A (en) * | 1984-06-27 | 1986-01-22 | Honshu Paper Co Ltd | Manufacture of high concentration solution of polyaluminum chloride having high basicity |
| CN1046512A (en) * | 1990-01-19 | 1990-10-31 | 刘振明 | Produce the method for polymerize aluminum chloride by aluminium hydroxide |
| DE4121276C2 (en) * | 1991-06-27 | 1994-02-17 | Metallgesellschaft Ag | Process for the preparation of sulfate-containing, basic polyaluminium chloride solutions |
| CA2229266C (en) * | 1995-09-18 | 2001-10-16 | Delta Chemical Corporation | Polyaluminum chlorides and polyaluminum chlorosulfates methods and compositions |
| EP0884279B1 (en) * | 1997-06-11 | 2002-07-24 | Akzo Nobel N.V. | A process for producing polyamminium chloride |
| CN1205306A (en) * | 1997-07-15 | 1999-01-20 | 吉林化学工业公司龙江净水剂厂 | Method of preparing polymerization aluminium chloride |
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