CN108796612A - A kind of method of ardealite Cycle-decomposition Sulphuric acid calcium pyroborate coproduction of ammonia sulfate - Google Patents
A kind of method of ardealite Cycle-decomposition Sulphuric acid calcium pyroborate coproduction of ammonia sulfate Download PDFInfo
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- CN108796612A CN108796612A CN201810574567.8A CN201810574567A CN108796612A CN 108796612 A CN108796612 A CN 108796612A CN 201810574567 A CN201810574567 A CN 201810574567A CN 108796612 A CN108796612 A CN 108796612A
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- Prior art keywords
- calcium
- filtrate
- ardealite
- sulfate
- sulfuric acid
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- 238000000034 method Methods 0.000 title claims abstract description 59
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000000354 decomposition reaction Methods 0.000 title claims abstract description 17
- GJYLKIZKRHDRER-UHFFFAOYSA-N calcium;sulfuric acid Chemical compound [Ca].OS(O)(=O)=O GJYLKIZKRHDRER-UHFFFAOYSA-N 0.000 title claims abstract description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims abstract description 82
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 74
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims abstract description 67
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000706 filtrate Substances 0.000 claims abstract description 59
- 239000013078 crystal Substances 0.000 claims abstract description 41
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims abstract description 36
- 235000011130 ammonium sulphate Nutrition 0.000 claims abstract description 36
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 36
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 239000002893 slag Substances 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000002425 crystallisation Methods 0.000 claims abstract description 25
- 239000012065 filter cake Substances 0.000 claims abstract description 24
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 18
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000011575 calcium Substances 0.000 claims abstract description 13
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 13
- 239000000047 product Substances 0.000 claims abstract description 13
- 239000000243 solution Substances 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000005864 Sulphur Substances 0.000 claims abstract description 9
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 20
- 239000000126 substance Substances 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 16
- 239000000908 ammonium hydroxide Substances 0.000 claims description 16
- 230000007062 hydrolysis Effects 0.000 claims description 15
- 238000006460 hydrolysis reaction Methods 0.000 claims description 15
- 239000012452 mother liquor Substances 0.000 claims description 12
- 229910021529 ammonia Inorganic materials 0.000 claims description 10
- 238000001914 filtration Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000004568 cement Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 5
- PASHVRUKOFIRIK-UHFFFAOYSA-L calcium sulfate dihydrate Chemical compound O.O.[Ca+2].[O-]S([O-])(=O)=O PASHVRUKOFIRIK-UHFFFAOYSA-L 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- PRKQVKDSMLBJBJ-UHFFFAOYSA-N ammonium carbonate Chemical compound N.N.OC(O)=O PRKQVKDSMLBJBJ-UHFFFAOYSA-N 0.000 claims description 2
- FYHXNYLLNIKZMR-UHFFFAOYSA-N calcium;carbonic acid Chemical compound [Ca].OC(O)=O FYHXNYLLNIKZMR-UHFFFAOYSA-N 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 238000006386 neutralization reaction Methods 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 abstract description 7
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 abstract description 7
- 235000012538 ammonium bicarbonate Nutrition 0.000 abstract description 7
- 239000001099 ammonium carbonate Substances 0.000 abstract description 7
- 239000006227 byproduct Substances 0.000 abstract description 6
- 239000011259 mixed solution Substances 0.000 abstract description 6
- 238000005265 energy consumption Methods 0.000 abstract description 5
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 238000004064 recycling Methods 0.000 abstract description 2
- 239000010703 silicon Substances 0.000 abstract description 2
- 229910052710 silicon Inorganic materials 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 235000011132 calcium sulphate Nutrition 0.000 description 27
- 239000002002 slurry Substances 0.000 description 13
- 239000007789 gas Substances 0.000 description 9
- 239000002253 acid Substances 0.000 description 8
- 230000008025 crystallization Effects 0.000 description 7
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 5
- HBYOLNPZXLHVQA-UHFFFAOYSA-J dicalcium dicarbonate Chemical compound [Ca+2].[Ca+2].[O-]C([O-])=O.[O-]C([O-])=O HBYOLNPZXLHVQA-UHFFFAOYSA-J 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000001175 calcium sulphate Substances 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229940088417 precipitated calcium carbonate Drugs 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 238000004513 sizing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 235000011941 Tilia x europaea Nutrition 0.000 description 1
- GCNLQHANGFOQKY-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4] GCNLQHANGFOQKY-UHFFFAOYSA-N 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 239000004566 building material Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- IKRMZAOEXULJQX-UHFFFAOYSA-N calcium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Ca+2].O1B([O-])OB2OB([O-])OB1O2 IKRMZAOEXULJQX-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002817 coal dust Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000002019 doping agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003337 fertilizer Substances 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000004571 lime Substances 0.000 description 1
- 229910001512 metal fluoride Inorganic materials 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000011295 pitch Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 239000004291 sulphur dioxide Substances 0.000 description 1
- 235000010269 sulphur dioxide Nutrition 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 229910052905 tridymite Inorganic materials 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
- C01—INORGANIC CHEMISTRY
- C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
- C01C1/00—Ammonia; Compounds thereof
- C01C1/24—Sulfates of ammonium
-
- 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
- C30B7/14—Single-crystal growth from solutions using solvents which are liquid at normal temperature, e.g. aqueous solutions the crystallising materials being formed by chemical reactions in the solution
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
- Processing Of Solid Wastes (AREA)
Abstract
The invention discloses a kind of methods of ardealite Cycle-decomposition Sulphuric acid calcium pyroborate coproduction of ammonia sulfate, specifically include following steps：（a）Ardealite is after sulfuric acid reaction cleans plus water is sized mixing into inversion of phases slot, reacts, filters with ammonium bicarbonate mixed solution, obtains ammonium sulfate solution I and calcium carbonate slag I；(b) calcium slag I adds nitric acid to decompose, filter to obtain white residue II and calcium nitrate filtrate II；(c) calcium nitrate filtrate II and sulfuric acid are reacted, crystallisation by cooling, filter to get filtrate III and filter cake III, and filter cake III is washed, dry that calcium sulfate crystal whiskers, filtrate II I remove cycle acidolysis calcium slag；（d）Ammonium sulfate filtrate is neutralized to after pH is 4.5 ~ 5.8 through sulfuric acid and removes vacuum concentration, crystallisation by cooling, dry ammonium sulfate.The present invention is not necessarily to high temperature, and the hierarchical synthesis for realizing sulphur in ardealite, calcium, silicon etc. at a lower temperature utilizes, and energy consumption is relatively low；Recycling for by-product is realized, secondary pollution is not generated, there is the preferable feature of environmental protection；Products therefrom ammonium sulfate and calcium sulfate product purity are higher, and application field is wider, have higher economic value.
Description
Technical field
The invention belongs to ardealite technical field of comprehensive utilization, and in particular to one kind is with ardealite, ammonium hydroxide and nitric acid and sulphur
Acid is the method that feedstock circulation decomposition prepares calcium sulfate crystal whiskers producing ammonium sulfate byproduct.
Background technology
Ardealite is sulfuric acid process phosphoric acid by wet process Main By product, main component CaSO4 2H 2O generally also contains in addition
8~15% SiO2And free acid, metal ion and fluoride etc., dopant species are more, and processing is relatively difficult.It is average often to give birth to
1 ton of phosphoric acid of production about generates 4.5 ~ 5.5 tons of ardealites, the whole world about 2 ~ 300,000,000 tons of discharge every year.China's sulphur dioxide of phosphor chemical industry is annual
About 50,000,000 tons of ardealite amount is discharged, and is still increased every year with 15% rate.Since ardealite yield is huge, and
Ardealite comprehensively utilizes the limitation of the market capacity of product（Utilization rate is less than 5%）, most of phosphatic compound fertilizer enterprise is by ardealite
Stockpiling processing mainly is done, this not only wastes valuable calcium, Sulphur ressource, but also is caused seriously to ground surface environment and ground water regime
Pollution, from environment and technical security angle, the comprehensive utilization of phosphogypsum slag is extremely urgent.
In existing technology, most of ardealite is mainly for the production of sulfuric acid and cement and plasterboard and sustained release agent
Equal building materials, also have part for producing potassium sulfate（Including wet method and Re Fa techniques）, but due to by cost of material, energy consumption
Deng limitation, fail in industry to promote；Also part of the manufacturer prepares ammonium sulfate with ardealite, but also have in by-product calcium carbonate compared with
More silica and acid non-soluble substance, this makes the quality of calcium carbonate not high, and application range is also relatively narrow, and economic value compared with
It is low.In order to further utilize calcium carbonate slag, new technical study has been carried out in succession, has been produced mainly for the preparation of the calcium carbonate of high activity
Product are sprayed into if 103524057 A of patent CN are disclosed using the by-product calcium carbonate of ardealite sulphur ammonium as raw material to dore furnace
The energy consumption of coal dust and air, the method that heat resolve obtains lime under 1200 DEG C of high-temperature flue gas, method processing is higher.Liu Jian（Liu
It is strong that nitrate leaching ardealite calcium slags is waited to prepare high-quality precipitated calcium carbonate [J] Environmental Chemistries, 2010,29 (4): 772-
773）Calcium slag is decomposed with nitric acid and obtains calcium nitrate, then is passed through carbon dioxide and preparing calcium carbonate, which needs to consume more nitric acid, at
This is higher.(the ardealite calcium slags such as Meng Tiehong prepare precipitated calcium carbonate technical study [J] chemical industry mineral and add Meng Tiehong etc.
Work, 2014,08:Calcium oxide obtained by high-temperature calcination ardealite 9-12.) is utilized, adds water to obtain calcium hydroxide, then be passed through titanium dioxide
Carbon prepares calcium carbonate, which need to calcine calcium slag and obtain calcium oxide, and energy consumption is higher.
Calcium sulfate crystal whiskers are a kind of microdenier staples, because with intensity height, toughness height, modulus height, high temperature resistant, wear-resisting, resistance to
The characteristic for corroding and being easy to surface treatment, suffers from industries such as papermaking, rubber, plastics, pitch, adhesives and widely answers
With.Currently, calcium sulfate crystal whiskers production mainly have normal pressure acidization and hydro-thermal reaction method, although hydro-thermal method research it is more due to by
Reaction temperature and the higher restriction of pressure, not yet industrialize at present.Normal pressure acidization generally obtains sulphur by acid dissolving, cold crystallization
Sour calcium pyroborate.As 104005086 B of patent CN disclose a kind of method of dissolving with hydrochloric acid preparing calcium sulphate whiskers from ardealite, but
The liquid-solid ratio of hydrochloric acid solution and calcium sulfate is larger, and power consumption is higher.(Cui Yi is along preparing calcium sulphate whiskers from ardealite by Cui Yishun
Research [J] inorganic chemicals industries, 2010,42 (9):Average major diameter 49-50.) is prepared for as raw material using sulfuric acid and ardealite
Than for 95 calcium sulfate crystal whiskers, but calcium sulfate crystal whiskers yield, purity and whiteness are relatively low, wherein whiteness 65.8%, purity are
93.6l%, yield 31.36%.
Invention content
For high energy consumption, by-product purity during overcoming the above method to handle ardealite and value of the product amount is low asks
Topic, the present invention is intended to provide a kind of low-temperature circulating decomposing phosphogypsum, prepares the calcium sulfate crystal whiskers and sulfuric acid of high-purity and draw ratio
The method of ammonium.
Realize the technical scheme is that, a kind of method of ardealite Cycle-decomposition Sulphuric acid calcium pyroborate coproduction of ammonia sulfate
Include the following steps：
（a）Inversion of phases process：Ardealite is filtered with dilute sulfuric acid impurity removal reaction, is washed to neutrality, is added water subsequently into inversion of phases slot
It sizes mixing, and is passed through the ammonium carbonate salt solution progress phase conversion reaction after ammonium hydroxide absorbs hydrolysis procedure tail gas, filters to obtain ammonium sulfate solution I
With thick calcium carbonate slag I；
(b) hydrolysis procedure：Nitric acid solution, filtering is added in thick calcium carbonate I, obtains slag II and calcium nitrate filtrate II；Slag II goes to produce
Cement, calcium nitrate filtrate are used to prepare calcium sulfate crystal whiskers, and tail gas goes ammonium hydroxide to absorb and is used for decomposing phosphogypsum；
(c) whisker preparation section：Calcium nitrate filtrate II is added after sulfuric acid through reaction, crystallisation by cooling, filters to obtain filter cake III and filter
Liquid III；Filter cake III is back to through washing, drying and obtaining calcium sulfate crystal whiskers, filtrate II I（b）Hydrolysis procedure is used for Cycle-decomposition carbonic acid
Calcium slag I；
（d）Sulphur ammonium process：Ammonium sulfate filtrate I adds sulfuric acid neutralization to be adjusted to remove Concentrated and crystallized in vacuum, dry sulphur after pH is 4.5 ~ 5.8
Ammonium product, concentration condensed water go inversion of phases process to size mixing and wash use.
Further, the mass ratio of the inversion of phases process, ardealite and total ammonia is 2.7 ~ 3.05：1, reaction temperature is
50 ~ 70 DEG C, mixing speed is 200 ~ 250r/min, and the reaction time is 1.5 ~ 2.5 h.
3. a kind of method of ardealite Cycle-decomposition Sulphuric acid calcium pyroborate coproduction of ammonia sulfate according to claim 1, special
Sign is：In the hydrolysis procedure, calcium carbonate slag I first adds water to size mixing, and is slow added into a concentration of 40 ~ 60% nitric acid and reacts,
It is 2.0 ~ 2.05 to control the ratio between amount of substance of nitric acid and calcium：1,70 ~ 80 DEG C of reaction temperature, mixing speed is 250 ~ 300r/
Min is filtered after 1.0 ~ 1.5h of reaction, obtains calcium nitrate filtrate II and filter residue II.
Further, the whisker preparation section,（1）Sulfuric acid and calcium nitrate filtrate are added simultaneously to reactive tank, sulfuric acid
It is 0.95 ~ 1.05 with the ratio between the amount of substance in calcium nitrate filtrate：1；
（2）Sulfuric acid is 80 ~ 95 DEG C, mixing speed 200r/min with calcic filtrate reaction temperature, and the reaction time is 1.0 ~ 1.5h；
（3）Reaction material liquid obtains filter cake and mother liquor, filter cake III is through washing, drying in 25 ~ 35 DEG C of crystallisation by cooling 1.5-2.0 h after filtering
Calcium sulfate crystal whiskers are done to obtain, filtrate II I, which is added after merging with wash water after concentrated nitric acid is adjusted to a concentration of 50 ~ 60%, goes hydrolysis procedure to recycle
Decompose calcium carbonate slag II.
Further, calcium sulfate crystal whiskers purity >=98% obtained by the whisker process, draw ratio >=45, whiteness >=
95%；
Further, filtrate obtained by the inversion of phases process is added 40 ~ 60% sulfuric acid and is adjusted to after pH value of solution is 4.5 ~ 5.5
It sends to and is concentrated in vacuo to pulp density as after 1.35 ~ 1.36 g/ml, crystallisation by cooling filters to obtain ammonium sulfate under the conditions of 58-60 DEG C
Crystal, after crystal is dry at 110 ~ 120 DEG C ammonium sulfate product, N content >=21.0% in gained ammonium sulfate product.
The present invention has the following advantages：
（1）The present invention is not necessarily to hot conditions, and the hierarchical synthesis that ardealite sulphur, calcium, silicon etc. are realized in lower temperature utilizes, energy
It consumes relatively low；
（2）The tail gas carbon dioxide that sour calcium process is absorbed using liquefied ammonia is used for Cycle-decomposition ardealite, and whisker filtrate cycle is decomposed
Calcium carbonate and sulphur ammonium process condensate water circulatory are washed and are sized mixing for ardealite, realize recycling for Industrial " three Waste ",
Secondary pollution is not generated, there is the preferable feature of environmental protection；
（3）Use the product obtained by decomposing phosphogypsum of the present invention higher for ammonium sulfate and calcium sulfate product purity, application field is more
Extensively, there is higher economic value.
Specific embodiment
Embodiment 1
A concentration of 30% sulfuric acid and ardealite are added into pretreatment tank, is 50 DEG C in temperature, mixing speed is 200r/min items
It is filtered after reacting 1.0 h under part, after filter cake adds water washing to neutrality, Belt Conveying to inversion of phases slot；By ardealite and total ammonia
Mass ratio is 2.95：1 the mixed solution of ammonium hydroxide and ammonium hydrogen carbonate is added into inversion of phases slot, and controlling reaction temperature is 70 DEG C,
It is reacted 2.0 hours under 200 r/min stirring conditions, obtains ammonium sulfate filtrate I after filtering and calcium carbonate calcium slag I, calcium carbonate slag I add water
After sizing mixing enter acidolysis slot, ammonium sulfate filtrate be added 40% sulfuric acid be adjusted to pH=5.0 after be concentrated into vacuum concentration system
Pulp density is 1.355g/L, slurry under the conditions of 60 DEG C crystallisation by cooling, centrifuge to obtain ammonia sulfate crystal, crystal is at 115 DEG C
The N content of lower dry ammonium sulfate, gained ammonium sulfate is 21.05%；The ratio between amount of substance by nitric acid and calcium carbonate is 2.05：1
Calcium carbonate slurry is added into acidolysis slot and 50% nitric acid, 70 DEG C of controlling reaction temperature are reacted under 250 r/min mixing speeds
Calcium nitrate filtrate II and white residue II is filtered to obtain after 1.0 hours, white residue goes to prepare cement, and calcium nitrate filtrate II removes next step whisker
Process utilizes, and tail gas goes 25% ammonium hydroxide to absorb；The ratio between amount by substance is n (H2SO4：Ca2+)=1.05：1 into whisker reactive tank
A concentration of 50 % sulfuric acid and calcium nitrate filtrate are added simultaneously, control reaction material liquid temperature is 80 DEG C, mixing speed 200r/min,
Enter crystallization tank after reacting 1.5 h, 2.0 h of crystallisation by cooling under the conditions of 25 DEG C obtains filter cake III and mother liquor after being filtered, washed
III, filter cake III are merged to obtain mother liquor III, are sent to acidolysis with calcium sulfate crystal whiskers, filtrate and wash water is dried to obtain after 70-80 DEG C of hot water wash
The thick calcium carbonate of process Cycle-decomposition.The draw ratio of gained calcium sulfate crystal whiskers is 48, purity 98.5%, whiteness 95.
Embodiment 2
Example 2 is similar to example 1, the difference is that, in inversion of phases process, the ammonia and ammonium hydrogen carbonate that are added in inversion of phases slot
Solution is that 25% ammonium hydroxide absorbs obtained by the tail gas of hydrolysis procedure, and the mass ratio of ardealite and total ammonia is 3：1；In hydrolysis procedure, it is added
Acid to be prepared by example 1 mother liquid obtained after calcium sulfate crystal whiskers（Or filtrate）, wherein acid concentration is 55%；In whisker preparation section, add
The sulfuric acid concentration entered is 40%, and the ratio between the amount of substance of sulfuric acid and calcium nitrate is n (H2SO4：Ca2+)=1.0：1, reaction solution is through cold
But calcium sulfate crystal whiskers, are obtained after crystallization filtering, whisker washs 25 DEG C of water washings.Using the condition, gained calcium sulfate crystal whiskers are long
Diameter ratio is 40, purity 97.5%, whiteness 95.
Embodiment 3
A concentration of 40% sulfuric acid and ardealite are added into pretreatment tank, is 40 DEG C in temperature, mixing speed is 200r/min items
It is filtered after reacting 1.5 h under part, after filter cake is washed to neutrality, inversion of phases slot is delivered to through belt；By the matter of ardealite and total ammonia
Amount is than being 3.05：1 the mixed solution of ammonium hydroxide and ammonium hydrogen carbonate is added into inversion of phases slot, and controlling reaction temperature is 60 DEG C, 250
It is reacted 2.0 hours under r/min stirring conditions, obtains ammonium sulfate filtrate I after filtering and calcium carbonate calcium slag I, calcium carbonate slag I add water to size mixing
Enter acidolysis slot afterwards, the sulfuric acid of ammonium sulfate filtrate addition 60% is adjusted to behind pH=4.5 is concentrated into slurry into vacuum concentration system
A concentration of 1.360g/L, slurry under the conditions of 58 DEG C crystallisation by cooling, centrifuge to obtain ammonia sulfate crystal, crystal is done at 120 DEG C
Dry to obtain ammonium sulfate, the N content of gained ammonium sulfate is 21.12%；The ratio between amount of substance by nitric acid and calcium carbonate is 2.0：1 to acid
Calcium carbonate slurry is added in solution slot and 45% nitric acid, 80 DEG C of controlling reaction temperature react 1.5 under 250 r/min mixing speeds
Calcium nitrate filtrate II and white residue II is filtered to obtain after hour, white residue goes to prepare cement, and calcium nitrate filtrate II goes next step whisker process
It utilizes, tail gas goes 20% ammonium hydroxide to absorb；The ratio between amount by substance is n (H2SO4：Ca2+)=0.95：1 into whisker reactive tank simultaneously
A concentration of 40% sulfuric acid and calcium nitrate filtrate is added, control reaction material liquid temperature is 95 DEG C, mixing speed 200r/min, reaction
Enter crystallization tank after 1.0 h, 1.5 h of crystallisation by cooling under the conditions of 35 DEG C obtains filter cake III and mother liquor III, filter after being filtered, washed
Calcium sulfate crystal whiskers are dried to obtain after 70-80 DEG C of hot water wash of cake III, filtrate and wash water merge to obtain mother liquor III, send to hydrolysis procedure and follow
Ring decomposes thick calcium carbonate.The draw ratio of gained calcium sulfate crystal whiskers is 45, purity 98.8%, whiteness 97.
Embodiment 4
A concentration of 40% sulfuric acid and ardealite are added into pretreatment tank, is 42-45 DEG C in temperature, mixing speed 200r/
It is filtered after reacting 1.5 h under the conditions of min, after filter cake is washed to neutrality, inversion of phases slot is delivered to through belt；By ardealite and total ammonia
Mass ratio be 2.7：1 the mixed solution of ammonium hydroxide and ammonium hydrogen carbonate is added into inversion of phases slot, and controlling reaction temperature is 70 DEG C,
It is reacted 2.0 hours under 250 r/min stirring conditions, obtains ammonium sulfate filtrate I after filtering and calcium carbonate calcium slag I, calcium carbonate slag I add water
Enter acidolysis slot after sizing mixing, the sulfuric acid of ammonium sulfate filtrate addition 60% is adjusted to after pH is 5.6 to be concentrated into vacuum concentration system
Pulp density is 1.360g/L, slurry under the conditions of 58 DEG C crystallisation by cooling, centrifuge to obtain ammonia sulfate crystal, crystal is at 120 DEG C
The N content of lower dry ammonium sulfate, gained ammonium sulfate is 21.24%；The ratio between amount of substance by nitric acid and calcium carbonate is 2.0：1
Calcium carbonate slurry is added into acidolysis slot and 45% nitric acid, 75 DEG C of controlling reaction temperature are reacted under 250 r/min mixing speeds
Calcium nitrate filtrate II and white residue II is filtered to obtain after 1.5 hours, white residue goes to prepare cement, and calcium nitrate filtrate II removes next step whisker
Process utilizes, and tail gas goes 20% ammonium hydroxide to absorb；The ratio between amount by substance is n (H2SO4：Ca2+)=0.95：1 into whisker reactive tank
A concentration of 40% sulfuric acid and calcium nitrate filtrate are added simultaneously, control reaction material liquid temperature is 95 DEG C, mixing speed 200r/min,
Enter crystallization tank after reacting 1.0 h, 1.5 h of crystallisation by cooling under the conditions of 35 DEG C obtains filter cake III and mother liquor after being filtered, washed
III, filter cake III are merged to obtain mother liquor III, are sent to acidolysis with calcium sulfate crystal whiskers, filtrate and wash water is dried to obtain after 70-80 DEG C of hot water wash
The thick calcium carbonate of process Cycle-decomposition.The draw ratio of gained calcium sulfate crystal whiskers is 44, purity 98.2%, whiteness 97.
Embodiment 5
A concentration of 40% sulfuric acid and ardealite are added into pretreatment tank, is 50 DEG C in temperature, mixing speed is 200r/min items
It is filtered after reacting 1 h under part, after filter cake is washed to neutrality, inversion of phases slot is delivered to through belt；By the quality of ardealite and total ammonia
Than being 2.80：1 the mixed solution of ammonium hydroxide and ammonium hydrogen carbonate is added into inversion of phases slot, and controlling reaction temperature is 70 DEG C, 250
It is reacted 1.5 hours under r/min stirring conditions, obtains ammonium sulfate filtrate I after filtering and calcium carbonate calcium slag I, calcium carbonate slag I add water to size mixing
Enter acidolysis slot afterwards, the sulfuric acid of ammonium sulfate filtrate addition 60% is adjusted to after pH is 5.8 is concentrated into slurry into vacuum concentration system
A concentration of 1.360g/L, slurry under the conditions of 58 DEG C crystallisation by cooling, centrifuge to obtain ammonia sulfate crystal, crystal is done at 120 DEG C
Dry to obtain ammonium sulfate, the N content of gained ammonium sulfate is 21.34%；The ratio between amount of substance by nitric acid and calcium carbonate is 2.0：1 to acid
It solves and calcium carbonate slurry and 45% nitric acid is added in slot, it is small to react 1 under 250 r/min mixing speeds for 80 DEG C of controlling reaction temperature
When after filter to obtain calcium nitrate filtrate II and white residue II, white residue goes to prepare cement, and calcium nitrate filtrate II goes next step whisker process sharp
With tail gas goes 20% ammonium hydroxide to absorb；The ratio between amount by substance is n (H2SO4：Ca2+)=0.95：1 adds simultaneously into whisker reactive tank
Enter a concentration of 40% sulfuric acid and calcium nitrate filtrate, control reaction material liquid temperature is 95 DEG C, mixing speed 200r/min, reaction 1.0
Enter crystallization tank after h, 1.5 h of crystallisation by cooling under the conditions of 35 DEG C obtains filter cake III and mother liquor III, filter cake III after being filtered, washed
With calcium sulfate crystal whiskers are dried to obtain after 70-80 DEG C of hot water wash, filtrate and wash water merge to obtain mother liquor III, send to hydrolysis procedure cycle point
Solve thick calcium carbonate.The draw ratio of gained calcium sulfate crystal whiskers is 46, purity 98.9%, whiteness 97.
Embodiment 6
A concentration of 40% sulfuric acid and ardealite are added into pretreatment tank, is 50 DEG C in temperature, mixing speed is 200r/min items
It is filtered after reacting 1.5 h under part, after filter cake is washed to neutrality, inversion of phases slot is delivered to through belt；By the matter of ardealite and total ammonia
Amount is than being 2.80：1 the mixed solution of ammonium hydroxide and ammonium hydrogen carbonate is added into inversion of phases slot, and controlling reaction temperature is 70 DEG C, 250
It is reacted 2 hours under r/min stirring conditions, ammonium sulfate filtrate I and calcium carbonate calcium slag I is obtained after filtering, after calcium carbonate slag I adds water to size mixing
Into acidolysis slot, the sulfuric acid that ammonium sulfate filtrate is added 60% is adjusted to after pH is 5.6 that into vacuum concentration system to be concentrated into slurry dense
Degree is 1.360g/L, slurry under the conditions of 58 DEG C crystallisation by cooling, centrifuge to obtain ammonia sulfate crystal, crystal is dry at 120 DEG C
Ammonium sulfate is obtained, the N content of gained ammonium sulfate is 21.5%；The ratio between amount of substance by nitric acid and calcium carbonate is 2.0：1 to acidolysis slot
Middle addition calcium carbonate slurry and 45% nitric acid, 80 DEG C of controlling reaction temperature, after being reacted 1 hour under 250 r/min mixing speeds
Calcium nitrate filtrate II and white residue II is filtered to obtain, white residue goes to prepare cement, and calcium nitrate filtrate II goes next step whisker process to utilize, tail
Gas goes 20% ammonium hydroxide to absorb；The ratio between amount by substance is n (H2SO4：Ca2+)=0.95：1 is added concentration simultaneously into whisker reactive tank
For 40% sulfuric acid and calcium nitrate filtrate, control reaction material liquid temperature is 95 DEG C, mixing speed 200r/min, and 1.0 h of reaction are laggard
Enter crystallization tank, crystallisation by cooling 2h under the conditions of 35 DEG C obtains filter cake III and mother liquor III, filter cake III 70-80 after being filtered, washed
Calcium sulfate crystal whiskers are dried to obtain after DEG C hot water wash, filtrate and wash water merge to obtain mother liquor III, send to the thick carbonic acid of hydrolysis procedure Cycle-decomposition
Calcium.The draw ratio of gained calcium sulfate crystal whiskers is 46, purity 98.7%, whiteness 97.
The above embodiments are only the preferred technical solution of the present invention, and are not construed as the limitation for the present invention, this Shen
Please in embodiment and embodiment in feature in the absence of conflict, mutually can arbitrarily combine.
Claims (6)
1. a kind of method of ardealite Cycle-decomposition Sulphuric acid calcium pyroborate coproduction of ammonia sulfate, it is characterized in that：Include the following steps：
（a）Inversion of phases process：Ardealite is filtered with dilute sulfuric acid impurity removal reaction, is washed to neutrality, is added water subsequently into inversion of phases slot
It sizes mixing, and is passed through the ammonium carbonate salt solution progress phase conversion reaction after ammonium hydroxide absorbs hydrolysis procedure tail gas, filters to obtain ammonium sulfate solution I
With thick calcium carbonate slag I；
(b) hydrolysis procedure：Nitric acid solution, filtering is added in thick calcium carbonate I, obtains slag II and calcium nitrate filtrate II；Slag II goes to produce
Cement, calcium nitrate filtrate are used to prepare calcium sulfate crystal whiskers, and tail gas goes ammonium hydroxide to absorb and is used for decomposing phosphogypsum；
(c) whisker preparation section：Calcium nitrate filtrate II is added after sulfuric acid through reaction, crystallisation by cooling, filters to obtain filter cake III and filter
Liquid III；Filter cake III is back to through washing, drying and obtaining calcium sulfate crystal whiskers, filtrate II I（b）Hydrolysis procedure is used for Cycle-decomposition carbonic acid
Calcium slag I；
（d）Sulphur ammonium process：Ammonium sulfate filtrate I adds sulfuric acid neutralization to be adjusted to remove Concentrated and crystallized in vacuum, dry sulphur after pH is 4.5 ~ 5.8
Ammonium product, concentration condensed water go inversion of phases process to size mixing and wash use.
2. a kind of method of ardealite Cycle-decomposition Sulphuric acid calcium pyroborate coproduction of ammonia sulfate according to claim 1, special
Sign is：The mass ratio of the inversion of phases process, ardealite and total ammonia is 2.7 ~ 3.05：1, reaction temperature is 50 ~ 70 DEG C, stirring
Speed is 200 ~ 250r/min, and the reaction time is 1.5 ~ 2.5 h.
3. a kind of method of ardealite Cycle-decomposition Sulphuric acid calcium pyroborate coproduction of ammonia sulfate according to claim 1, it is characterized in that：
In the hydrolysis procedure, calcium carbonate slag I first adds water to size mixing, and is slow added into a concentration of 40 ~ 60% nitric acid and reacts, control
The ratio between amount of substance of nitric acid and calcium is 2.0 ~ 2.05：1,70 ~ 80 DEG C of reaction temperature, mixing speed is 250 ~ 300r/min, is waited for
It is filtered after 1.0 ~ 1.5h of reaction, obtains calcium nitrate filtrate II and filter residue II.
4. a kind of method of ardealite Cycle-decomposition Sulphuric acid calcium pyroborate coproduction of ammonia sulfate according to claim 1, it is characterized in that：
The whisker preparation section,（1）Sulfuric acid and calcium nitrate filtrate are added simultaneously to reactive tank, sulfuric acid and substance in calcium nitrate filtrate
The ratio between amount be 0.95 ~ 1.05：1；
（2）Sulfuric acid is 80 ~ 95 DEG C, mixing speed 200r/min with calcic filtrate reaction temperature, and the reaction time is 1.0 ~ 1.5h；
（3）Reaction material liquid obtains filter cake and mother liquor, filter cake III is through washing, drying in 25 ~ 35 DEG C of crystallisation by cooling 1.5-2.0 h after filtering
Calcium sulfate crystal whiskers are done to obtain, filtrate II I, which is added after merging with wash water after concentrated nitric acid is adjusted to a concentration of 50 ~ 60%, goes hydrolysis procedure to recycle
Decompose calcium carbonate slag II.
5. a kind of method of ardealite Cycle-decomposition Sulphuric acid calcium pyroborate coproduction of ammonia sulfate according to claim 1, it is characterized in that：
Calcium sulfate crystal whiskers purity >=98% obtained by the whisker process, draw ratio >=45, whiteness >=95%.
6. a kind of method of ardealite Sulphuric acid calcium pyroborate coproduction of ammonia sulfate according to claim 1, it is characterized in that：The phase
The sulfuric acid of filtrate addition 40 ~ 60% obtained by conversion procedure, which is adjusted to send to after pH value of solution is 4.5 ~ 5.5, is concentrated in vacuo to pulp density
After 1.35 ~ 1.36 g/ml, crystallisation by cooling filters to obtain ammonia sulfate crystal under the conditions of 58-60 DEG C, and crystal is done at 110 ~ 120 DEG C
After dry ammonium sulfate product, N content >=21.0% in gained ammonium sulfate product.
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