CN105084335A - Cogeneration method for producing monopotassium phosphate and potassium diformate - Google Patents
Cogeneration method for producing monopotassium phosphate and potassium diformate Download PDFInfo
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- CN105084335A CN105084335A CN201410197921.1A CN201410197921A CN105084335A CN 105084335 A CN105084335 A CN 105084335A CN 201410197921 A CN201410197921 A CN 201410197921A CN 105084335 A CN105084335 A CN 105084335A
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- potassium
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- formiate
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- BINNZIDCJWQYOH-UHFFFAOYSA-M potassium;formic acid;formate Chemical compound [K+].OC=O.[O-]C=O BINNZIDCJWQYOH-UHFFFAOYSA-M 0.000 title claims abstract description 61
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 46
- 229910000402 monopotassium phosphate Inorganic materials 0.000 title abstract 4
- 235000019796 monopotassium phosphate Nutrition 0.000 title abstract 4
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 title abstract 4
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 title abstract 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims abstract description 126
- WFIZEGIEIOHZCP-UHFFFAOYSA-M potassium formate Chemical compound [K+].[O-]C=O WFIZEGIEIOHZCP-UHFFFAOYSA-M 0.000 claims abstract description 106
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 86
- 239000007788 liquid Substances 0.000 claims abstract description 71
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims abstract description 63
- 235000019253 formic acid Nutrition 0.000 claims abstract description 63
- 238000000034 method Methods 0.000 claims abstract description 61
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 42
- 239000012452 mother liquor Substances 0.000 claims abstract description 22
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 21
- 239000006227 byproduct Substances 0.000 claims abstract description 11
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000007789 gas Substances 0.000 claims description 148
- 239000000463 material Substances 0.000 claims description 103
- 239000007921 spray Substances 0.000 claims description 85
- 238000003860 storage Methods 0.000 claims description 71
- 239000000047 product Substances 0.000 claims description 61
- 238000003786 synthesis reaction Methods 0.000 claims description 55
- 230000015572 biosynthetic process Effects 0.000 claims description 52
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 48
- 229910052700 potassium Inorganic materials 0.000 claims description 48
- 239000011591 potassium Substances 0.000 claims description 48
- 229910019142 PO4 Inorganic materials 0.000 claims description 47
- 239000010452 phosphate Substances 0.000 claims description 47
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 46
- 238000003756 stirring Methods 0.000 claims description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 230000008569 process Effects 0.000 claims description 31
- 238000010521 absorption reaction Methods 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000009833 condensation Methods 0.000 claims description 27
- 230000005494 condensation Effects 0.000 claims description 27
- 238000000746 purification Methods 0.000 claims description 22
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical compound [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 21
- 238000004821 distillation Methods 0.000 claims description 20
- 238000001704 evaporation Methods 0.000 claims description 19
- 238000002844 melting Methods 0.000 claims description 19
- 230000008018 melting Effects 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 19
- 238000002347 injection Methods 0.000 claims description 18
- 239000007924 injection Substances 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 18
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 17
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 17
- 239000003245 coal Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 14
- 239000003513 alkali Substances 0.000 claims description 13
- 239000013078 crystal Substances 0.000 claims description 12
- 230000000694 effects Effects 0.000 claims description 12
- 238000005192 partition Methods 0.000 claims description 12
- 239000000428 dust Substances 0.000 claims description 10
- 230000002459 sustained effect Effects 0.000 claims description 10
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 9
- 239000011575 calcium Substances 0.000 claims description 9
- 229910052791 calcium Inorganic materials 0.000 claims description 9
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 9
- 239000011707 mineral Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 8
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 7
- 230000008025 crystallization Effects 0.000 claims description 7
- 238000009826 distribution Methods 0.000 claims description 7
- 230000008676 import Effects 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 7
- -1 Step 3 Substances 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 6
- 238000010992 reflux Methods 0.000 claims description 6
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims description 5
- 235000011089 carbon dioxide Nutrition 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000010304 firing Methods 0.000 claims description 5
- 235000003599 food sweetener Nutrition 0.000 claims description 5
- 239000003765 sweetening agent Substances 0.000 claims description 5
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 4
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 238000005108 dry cleaning Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 238000007789 sealing Methods 0.000 claims description 3
- 238000007514 turning Methods 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 238000005660 chlorination reaction Methods 0.000 claims description 2
- 230000018044 dehydration Effects 0.000 claims description 2
- 238000006297 dehydration reaction Methods 0.000 claims description 2
- 238000001556 precipitation Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 238000009423 ventilation Methods 0.000 claims 1
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000002194 synthesizing effect Effects 0.000 abstract description 2
- 229910002090 carbon oxide Inorganic materials 0.000 abstract 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 34
- 230000009102 absorption Effects 0.000 description 22
- 239000012071 phase Substances 0.000 description 14
- 238000001035 drying Methods 0.000 description 12
- 230000008020 evaporation Effects 0.000 description 12
- 239000001257 hydrogen Substances 0.000 description 12
- 229910052739 hydrogen Inorganic materials 0.000 description 12
- 235000011121 sodium hydroxide Nutrition 0.000 description 12
- 230000008859 change Effects 0.000 description 11
- 238000012545 processing Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 229910001220 stainless steel Inorganic materials 0.000 description 9
- 239000010935 stainless steel Substances 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 235000010755 mineral Nutrition 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 238000000926 separation method Methods 0.000 description 7
- 239000005997 Calcium carbide Substances 0.000 description 6
- 239000003337 fertilizer Substances 0.000 description 6
- 239000004800 polyvinyl chloride Substances 0.000 description 6
- 229920000915 polyvinyl chloride Polymers 0.000 description 6
- 235000002639 sodium chloride Nutrition 0.000 description 6
- 238000005507 spraying Methods 0.000 description 6
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 6
- 235000012255 calcium oxide Nutrition 0.000 description 5
- 238000005553 drilling Methods 0.000 description 5
- 150000003016 phosphoric acids Chemical class 0.000 description 5
- HLBBKKJFGFRGMU-UHFFFAOYSA-M sodium formate Chemical compound [Na+].[O-]C=O HLBBKKJFGFRGMU-UHFFFAOYSA-M 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000000967 suction filtration Methods 0.000 description 4
- 239000000725 suspension Substances 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000033228 biological regulation Effects 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- AHHYEKPJZYDDFK-UHFFFAOYSA-N formic acid;phosphoric acid Chemical compound OC=O.OP(O)(O)=O AHHYEKPJZYDDFK-UHFFFAOYSA-N 0.000 description 3
- 239000007952 growth promoter Substances 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000004568 cement Substances 0.000 description 2
- 239000012141 concentrate Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001873 dinitrogen Inorganic materials 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000002360 explosive Substances 0.000 description 2
- 239000012065 filter cake Substances 0.000 description 2
- 150000002431 hydrogen Chemical group 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000012423 maintenance Methods 0.000 description 2
- 238000010907 mechanical stirring Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000000618 nitrogen fertilizer Substances 0.000 description 2
- 230000001937 non-anti-biotic effect Effects 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 description 2
- 230000007306 turnover Effects 0.000 description 2
- 238000009834 vaporization Methods 0.000 description 2
- 230000008016 vaporization Effects 0.000 description 2
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 206010068516 Encapsulation reaction Diseases 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 208000027418 Wounds and injury Diseases 0.000 description 1
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 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
- GBAOBIBJACZTNA-UHFFFAOYSA-L calcium sulfite Chemical compound [Ca+2].[O-]S([O-])=O GBAOBIBJACZTNA-UHFFFAOYSA-L 0.000 description 1
- 235000010261 calcium sulphite Nutrition 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000005262 decarbonization Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000284 extract Substances 0.000 description 1
- 230000004720 fertilization Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001535 kindling effect Effects 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 235000013372 meat Nutrition 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- QVLTXCYWHPZMCA-UHFFFAOYSA-N po4-po4 Chemical compound OP(O)(O)=O.OP(O)(O)=O QVLTXCYWHPZMCA-UHFFFAOYSA-N 0.000 description 1
- 235000015277 pork Nutrition 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 229910001950 potassium oxide Inorganic materials 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 239000002893 slag Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- GOLXNESZZPUPJE-UHFFFAOYSA-N spiromesifen Chemical compound CC1=CC(C)=CC(C)=C1C(C(O1)=O)=C(OC(=O)CC(C)(C)C)C11CCCC1 GOLXNESZZPUPJE-UHFFFAOYSA-N 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000005829 trimerization reaction Methods 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/10—Process efficiency
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a cogeneration method for producing monopotassium phosphate and potassium diformate. The method comprises: synthesizing an "alkaline potassium formate synthetic liquid" by using inexpensive exhaust gas carbon oxide from a submerged arc furnace and potassium hydroxide; reacting phosphoric acid with potassium formate to producing monopotassium phosphate and a by-product formic acid; and using the formic acid and potassium formate to synthesize potassium diformate, wherein an ''acid mother liquor'' is a by-product and is recycled to neutralize the ''synthetic liquid'' for reducing alkalinity. Compared with the prior art, the technical solution provided by the present invention forms an industry chain to cogenerate potassium diformate and monopotassium phosphate so as to achieve the technical objectives of environmental protection, energy saving and clean production.
Description
Technical field
The present invention relates to a kind of method of producing potassium primary phosphate coproduction Potassium hydrogen diformate, more particularly, relate to carbon monoxide and potassium hydroxide and synthesize alkaline potassium formiate and synthesize liquid, produce the method for potassium primary phosphate coproduction Potassium hydrogen diformate with phosphatase reaction.
Background technology
The production of China's formate is in the fifties in last century of suitability for industrialized production by the organic synthesis factory of Tianjin, and progressively with the mode of exchange of technology assistance be other oxalic acid, formic acid, vat powder manufacturer provide free technical service, improves the integrated artistic technical equipment production level of China's formate.The beginning of the nineties in last century is due to the drilling well of international petroleum drilling well employing potassium formiate preparation drilling fluid, achieve drilling well, guide-well, the desirable drilling oil well of environment-friendly type, Tianjin organic synthesis factory requires by the Ministry of Chemical Industry: in original sodium formiate synthesis technique Equipment Foundations, transform the production of part processing equipment synthesis potassium formate product achieve successfully, along with Product Process technology, the updating and improve of quality, have accumulated a lot of processing unit production technology experience.
Potassium hydroxide production technology is very ripe, potassium hydroxide processing unit and sodium hydroxide production process equipment just the same, the just difference of raw materials used Repone K and sodium-chlor, but sodium hydroxide production capacity now, produce market is seriously superfluous, if utilize the process unit of existing electrolytic sodium chloride coproduct hydrogen sodium oxide to change raw material for Repone K can produce potassium hydroxide, PVC (polyvinyl chloride) due to China more than 70% produces with calcium carbide route, the electrolyze table salt hydrogenchloride that produces and the acetylene gas that produces of calcium carbide synthesizes PVC coproduct hydrogen sodium oxide production capacity, produce market is superfluous serious, same device is used for the potassium hydroxide of the production market requirement, feed change Repone K is reach identical hydrogenchloride output, the corresponding potassium hydroxide output value, the yields have increased considerably, and alleviate the selling market of sodium hydroxide, electrolyze table salt in recent years, closed calcium carbide furnace, PVC, the large-scale centralized of cement industry device is produced, for the reliability of environment protection treating becomes possibility, carbide slag wherein becomes a reality for the production of cement, the wet-dry change purification of calcium carbide stove exhaust consumes again the waste water produced in large-scale centralized Chemical Manufacture, potassium hydroxide as by-product can with the addition of again a bit beautiful energy-saving clean production technique to large-scale centralized production equipment with mineral hot furnace End gas production potassium primary phosphate and Potassium hydrogen diformate again.The synthesis technology of formate is very general ripe, but basic all need adding water in 32% concentration to alkali used is made into the alkaline solution of convenient operation, solution alkali content is generally about 15 ~ 25%, manual operation control synthesis liquid caustic soda content is very unstable and control alkali content is on the low side or neutral intentionally, often synthesizes, evaporates the phenomenon of etching apparatus like this in processing unit is produced.
China is big country based on agricultural, grain-production big country, chemical fertilizers production big country, the utilization ratio of chemical fertilizer only 30 ~ 40%, that 60 ~ 70% side effect brought simultaneously is very surprising, composite fertilizer's potassium primary phosphate deserves to be called in chemical fertilizer " fertile essence " to farm crop be 100% absorption, be free from side effects, let alone the injury to soil and environment, due to the price of its perfect effect and great number, unique people utilizes fake products to enrich market and leads peasant into a trap, and the price of fake products and great number has damaged the universal utilization in " fertile essence " potassium primary phosphate market.Namely China's 1,800,000,000 mu of every mu, good farmlands fertilising 10 kg of phosphoric acid potassium dihydrogens and 25 kilograms of nitrogenous fertilizer reach the fertilizer efficiency of required for farm crop 1 year, and (" increasing yield of potassium primary phosphate and effect " that Jiaozuo Univ. chemical institute chief Wang Dongtou writes is if change the fertilizing method of China, year fertilising potassium primary phosphate 1,800 ten thousand tons, this numerical value and China's year, the amount of 7,000 ten thousand tons to fertilize (main nitrogenous fertilizer urea) was suitable, but effect is completely different, potassium primary phosphate is used for the problem applied fertilizer without any side effect and contaminate environment in good farmland, fruit quality is better than other fertilization effect.
The method that existing known industry utilizes carbon monoxide production chemical product formate to add phosphoric acid formic acid and phosphoric acid byproduct salt has Chinese patent, CN101665423A, CN1179413A, CN101367718A (invalid patent), CN1994999A (invalid patent) discloses the method for multiple phosphoric acid formate, the requirement without exception of these methods obtains formic acid and the phosphoric acid byproduct salt of high density, after producing formic acid remaining phosphoric acid salt regulate the ratio of P/K to make the phosphoric acid salt of high added value again, it is huge that the formic acid producing high density makes the process of phosphoric acid formate become processing unit, operational condition is severe, equipment stir difficulty heat formic acid vaporization, phosphoric acid salt encapsulation reaction is half-cooked, the phosphoric acid salt produced can not be directly used in commercial phosphoric acid potassium dihydrogen, also broken must regulate ratio and the recrystallize of P/K in a kettle. again, be separated, dry potassium primary phosphate or again calcining obtain trimerization, six inclined commercial phosphoric acid salt, cause manpower like this, the input again of material resources.
The formic acid wanting to produce high-content must obtain the phosphoric acid of high-content and high-content on raw material formate, in formate, sodium formiate ratio is easier to evaporation, dry, make water-content lower than 0.5% sodium formiate finished product, alkali content lower than 0 ~ 0.05% time force the excessive formate solution that causes of carbon monoxide to become neutral for the deficiency of synthesis formate solution alkali, because the formate of the slow-releasing normal temperature neutrality of formate shows strongly-acid etching apparatus when high temperature, (formate solution has redness again, the colors such as grey), excessive carbon monoxide is discharged by release of pressure after synthesis reaction system, cause raw material like this, the loss of energy and the heavy corrosion of equipment, coloured formate solution inside forms polymkeric substance and is difficult to be processed into qualified formate solution, the potassium formiate content that CN101665423A considers is higher than 95%, phosphorus acid content just can obtain the formic acid product of GB/T2093-2011 commodity minimum content 85% higher than 96%.They use the phosphoric acid (wherein phosphorus pentoxide content is 61.58%) of commercially available 85% content without any a kind of example, the phosphoric acid of high density needs high energy consumption manufacture, for the formic acid products C N1179413A producing more than 85% content introduces the phosphoric acid that subsistence level uses content more than 96%.
Potassium formiate is evaporated to mass content 90% than being easier to, reconcentration is more difficult because potassium formiate solubleness (being similar to sodium hydroxide) is far above sodium formiate, potassium formiate content needs high temperature (250 DEG C) to concentrate more than 90%, so concentration technology is similar to the concentrated of caustic soda sodium hydroxide, being evaporated to certain value needs the heating of the concentrated high-temperature steam of high temperature, high temperature heat conductive oil or naked light enamelware pot concentrated, and energy consumption is far above sodium formiate.
Just nearly 20 years are researched and produced and used to Potassium hydrogen diformate, but tempo is very fast, it is the product of a kind of novel " microbiotic growth promoter " surrogate, the report " research that non-antibiotic growth stimulant Potassium hydrogen diformate affects pig growth performance " of the outstanding experimental study of Tianjin City Livestock Raising and Veterinary Inst. chief Wang Wen was issued in 2006, test and completed in 2004, wherein Potassium hydrogen diformate is provided by BASF Corp. of Germany, so far mention this Wang Wen outstanding person and remember clearly " experiment pork is very nice ", before associating our athlete's like this, long time can not eat meat (urine examination is positive).Calendar year 2001, European Union's approval uses Potassium hydrogen diformate, and this is the first non-antibiotic fodder additives for substitute antibiotics growth promoter of European Union's approval.European Union in 1 day January in 2006 completely forbid in feed, use microbiotic growth promoter, China on March 22nd, 2005 Ministry of Agriculture have approved Potassium hydrogen diformate as a kind of novel fodder additive in pig feed.According to Wang Wen outstanding person, China's feedstuff industry output last year 200000000 tons, considers that the minimum addition of feed controls 0.6%, year feed add the Potassium hydrogen diformate market close to 1,200,000 tons.
Existing known China patent: CN1704304A, CN1844074A, CN101125809A is with formic acid and alkali-metal oxide compound substantially, oxyhydroxide or corresponding reactant salt, configure different apparatus and process and produce Potassium hydrogen diformate, by evaporation, water is steamed system after reaction, improve the content of Potassium hydrogen diformate, their reaction is excessive with formic acid substantially, a kind of soln using evaporation is like this separated moisture and has any problem: formic acid and water when evaporating can with the form of azeotropic from liquid phase to gas phase again through condensation, cooling obtains containing first aqueous acid, such process loss formic acid and the water discharge steamed are subject to the pressure of environmental protection.US Patent No. 6137005 (the open CN1187807A of China) is mainly reacted with the potassium formate solutions of content 80 ~ 95% formic acid and content 70 ~ 80%, it is finished product that separation obtains crystal Potassium hydrogen diformate drying, mother liquor gets rid of with evaporation the potassium formate solutions that moisture obtains content 70 ~ 80% by 50% potassium hydroxide again, such process loss problem of high energy potassium hydroxide cascade utilization, corresponding energy consumption consumes (thermal pollution) with not available low-temperature heat source greatly, reaction is fierce dangerous, product is more single, the discharge of evaporation technology water produces environmental issue, the unicity of existing patented technology has limited to small-scale and the environmental issue of its production capacity.
It is high that domestic patent thinks that formic acid and potassium formiate produce Potassium hydrogen diformate cost, China's former commercially available potassium formiate in 2006 is the product synthesized with formic acid and potassium hydroxide substantially, can be thought of as that this is very high, price is not low, produce Potassium hydrogen diformate with it and there is no the market competitiveness equally, let alone universal Potassium hydrogen diformate is used as fodder additives.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, the composition problem of formate is synthesized for potassium hydroxide in prior art and carbon monoxide, a kind of method of producing potassium primary phosphate coproduction Potassium hydrogen diformate is provided, mineral hot furnace tail gas is utilized to produce with cheap purification cost the phosphoric acid that carbon monoxide raw material produces with chlor-alkali industry coproduct hydrogen potassium oxide and the phosphorous chemical industry of production capacity surplus for carbon one products material gas again, form the industrial chain of cleaner production, environment protection treating, Poly-generation low cost, produce the potassium primary phosphate of market demand and the method for Potassium hydrogen diformate.
Technical purpose of the present invention is achieved by following technical proposals:
Produce the method for potassium primary phosphate coproduction Potassium hydrogen diformate, comprise the steps:
Step 1, utilizes mineral hot furnace tail gas to purify, to make the volume fraction of carbon monoxide in tail gas more than 70%;
In described step 1, the method of dry cleaning and/or wet purification is adopted to process mineral hot furnace tail gas, consult and authorize the method for purification mineral hot furnace tail gas in patent of invention " enclosed ore-smelting furnace tail gas purification method for Chemicals are produced " to purify, to control the volume fraction of carbon monoxide in tail gas, reduce the content of other compositions to minimum (application number 2011100623155, March 15 2011 applying date) simultaneously; After the precipitation obtained in dry cleaning and/or wet purification process, dust, coal slime mix, mix the sweetening agent (the unslaked lime sweetening agent such as used in coal firing boiler) being used as coal firing boiler with fire coal.
Step 2, the aqueous solution of the gas of carbon monoxide volume fraction step 1 obtained more than 70% and potassium hydroxide carries out reaction and generates alkaline potassium formiate and synthesize liquid, and it is excessive to control potassium hydroxide, to guarantee that carbon monoxide all participates in the synthesis of alkaline potassium formiate synthesis liquid;
In described step 2, employing chlor-alkali industry electrolytic chlorination potassium byproduct weight percentage composition reacts at the potassium hydroxide aqueous solution of 32%, and is precisely controlled by DCS, to make reacted potassium hydroxide content between 3 ~ 10g/L; In step 2, the alkaline potassium formiate synthesis liquid of final synthesis enters in storage element;
Described storage element is that storage tank blending device is made up of burden storage tank and pump, tank interior conduit is set in burden storage tank, be connected with pump by pipeline at the bottom of the tank of burden storage tank, pump is connected with the tank interior conduit entrance of burden storage tank tank deck by another road pipeline, described tank interior conduit and burden storage tank height basically identical, the injection pipe be connected with tank interior conduit is from top to bottom evenly set, quantity is preferably 3-6, the sectional area summation of described injection pipe is equivalent to tank interior conduit sectional area, the outlet of injection pipe is 90 ~ 135 ° with the angle a of the tank interior conduit vertically arranged, in injection pipe exit, liquid sprays downwards with tangential direction concentrically ringed on burden storage tank cross section, to facilitate the mixture accelerating whole material.Adopt spray regime to replace traditional mechanical stirring, adopt reflux type carry out the circulation of material and fully mix, alkaline potassium formiate synthesis liquid circulates in storage element, simultaneously in the acidic substance that formed in subsequent step.
Step 3, potassium hydroxide excessive in alkaline potassium formiate synthesis liquid produced by Potassium hydrogen diformate formic acid gas that the acid mother liquid that produces and spray of negative pressure baker produce carry out in and, detect in the alkaline potassium formiate synthesis liquid of storage element: potassium formiate content is more than 400-800g/L, potassium hydroxide content is down between 1 ~ 5g/L, the alkaline potassium formiate synthesis liquid of storage element is evaporated, the potassium formiate of the molten state of weight percentage more than 90% can be obtained, utilize the potassium formiate (temperature about 150 DEG C of described molten state, such as 120-160 DEG C) and mass percentage 85% normal temperature phosphoric acid respectively by pump enter first pipeline reactor reaction to obtain potassium primary phosphate, material after reacting completely enters the first crystallizer, forms regular potassium primary phosphate xln, after being separated by the first separator: crystal enters the first spray of negative pressure baker and obtains product potassium primary phosphate, mother liquor is after distillation, vapor condensation obtains the formic acid of mass percentage 50 ~ 70%, the raffinate obtained at the bottom of still kettle is back in pipeline reactor, and wherein the gas phase of the first spray of negative pressure baker enters the first absorption tower, and alkaline potassium formate solutions circulates between the first absorption tower and storage element, mother liquor is after distillation, and vapor condensation obtains the formic acid of mass percentage 50 ~ 70% after purification, condensation receive, and is connected respectively with second pipe reactor with second absorption tower,
In described step 3, the alkaline potassium formiate synthesis liquid of storage element is carried out evaporating to obtain liquid potassium formiate; In described step 3, the potassium formiate evaporating the molten state of the weight percentage more than 90% obtained enters spray of negative pressure moisture eliminator and processes, to obtain potassium formate product after dissolving is concentrated.
In described step 3, mother liquor is after distillation, and vapor condensation obtains the formic acid of mass percentage 50 ~ 70% after purification, condensation receive, and by concentrated, to obtain product formic acid, also can be obtained by reacting product calcium formiate with calcium oxide.
Step 4, the potassium formiate of the molten state of the weight percentage more than 90% that step 3 obtains and the formic acid of mass percentage 50 ~ 70% enter second pipe reactor reaction to obtain Potassium hydrogen diformate respectively by pump, the material reacted completely enters the second crystallizer crystallization, form regular Potassium hydrogen diformate xln, be separated by the second separator: be separated mother liquor and go to be provided with in the storage element of alkaline potassium formiate synthesis liquid and alkaline potassium formiate synthesis liquid; Xln enters the second spray of negative pressure baker and obtains product Potassium hydrogen diformate, and gas phase enters second absorption tower, and alkaline potassium formate solutions circulates between second absorption tower and storage element.
In described step 3 and 4, the the first and second pipeline reactor structures used are consistent, the top of described pipeline reactor is adopted to realize circulating by pipeline and condenser, circulate to make formic acid and participate in reaction, the material participating in reaction enters from pipeline reactor lower end, and reacted material autoreaction material outlet flows out; Arrange four material feeding mouths at pipeline reactor lower end edge even circumferential, four the material feeding mouths being positioned at sustained height form one deck material feeding mouth, preferably 2-5 layers, described material feeding mouth; The described material feeding mouth being positioned at sustained height is consistent with horizontal direction angle, preferably 10-45 °; Be positioned at the tangential direction charging of material feeding mouth with tubular reactor circumference of sustained height, wherein phosphoric acid and melting potassium formiate are respectively from the material feeding mouth charging be positioned at angular direction, another two be positioned to the material feeding mouth of angular direction for vinasse charging (namely phosphoric acid and melting potassium formiate respectively diagonal angle A, C or B, D import enter, other two mouthfuls are entered vinasse); Described pipeline reactor adopts cylinder shape aspect ratio to be 2 ~ 50:1, upper and lower two ends adopt normal ellipsoidal head shutoff, and with heat exchange jacket, top with vapor condensation interchanger, phlegma can control the sealing load balance liquid seal apparatus refluxing and take out system of leaving.Material feeding pressure is 2 ~ 10 times of cylindrical reactor height (i.e. tubular reactor height) water column.
In step 3 and 4, the first and second mold structures of use are consistent, and select with jacket heat-exchanger, top with the airtight crystallization apparatus of vapor condensation interchanger and whipping appts, material enters material, bottom discharge by top
In step 3 and 4, the first and second cyclone separator arrangements of use are consistent, select airtight separating centrifuge to increase adapter and valve at its top.
In step 3, the distillation plant used adopts band to stir, the still distillation device of jacket steam heating, negative pressure of vacuum operation in still, gas phase is purified to condenser condenses through purification pot and obtains liquid formic acid for Potassium hydrogen diformate production, described purification pot is jacket steam heating and thermal insulation and water quench two cover system, certain potassium formiate and formic acid mixing solutions (mother liquor from separator) liquid level is kept to make formic acid gas pass through liquid in tank, wherein phosphate radical enters solution and is absorbed, the absorption of this solution reaches concentration requirement and removes the first pipeline reactor, after gas phase enters condenser condenses after purification, tail gas enters second absorption tower.
In described step 3 and 4, the first and second spray of negative pressure baker structures of use are consistent, the gas that chuck heat source and paddle spray into the former be high temperature, be oven drying at low temperature afterwards.Described spray of negative pressure baker is made up of spray tower and baker.Described spray tower is cylinder shape aspect ratio is between the general diameter of 2 ~ 10:1 1 ~ 10 meter, feeder, rotating centrifugal distributor and vacuum port are set at spray tower top, described feeder is connected with pipeline, and select feeding screw to enter in spray tower by mass transport to be dried, through the effect of rotating centrifugal distributor, to make material be uniformly distributed, and vacuum port is utilized to carry out vacuumizing process.Crystal after described feeding screw import receives centrifugation adds material seal apparatus in course of conveying, has completely cut off spray of negative pressure moisture eliminator and extraneous gas intercommunication.
Existing rake type dryer selected by described baker, be made up of dram, Heat exchange jacekt, air-cored axis and agitating unit, described dram is drum, and be connected with the lower end of spray tower by being arranged on the interface in dram, the lower end of described dram arranges product outlet; Described Heat exchange jacekt parcel dram, arranges steam inlet in Heat exchange jacekt upper end, arranges condensation-water drain (after heat exchange, steam flows out from condensation-water drain with water of condensation form) in Heat exchange jacekt lower end.In dram, concentric shafts arranges air-cored axis, two ends and the dram sidewall of air-cored axis are fixedly linked, compared with driving the turning axle of agitating unit in existing rake type dryer, at the center of whole air-cored axis, cross partition is set, cross partition is arranged along the axis of air-cored axis, four spaces do not communicated with each other to make the internal space of whole air-cored axis be split as, for transport gas (gas of use is inert nitrogen gas, carbonic acid gas, helium or argon gas, reaches explosive range to avoid oxygen); The outer wall being positioned at the air-cored axis of the outer side of dram sidewall along the circumferential direction arranges four inlet mouths, four gas circuits (space that namely cross partition four of being divided into are obstructed each other) of described four inlet mouths corresponding tubular shaft inside respectively, the tubular shaft of this side is ventilate in four spaces of air-cored axis's internal detachment; In air-cored axis, circumferentially agitating unit is set, described agitating unit adopts the rake stirring rake of rake baker (also known as vacuum rake type dryer), rake stirring rake arranges four rows along tubular shaft axial direction due, a gas circuit in the corresponding tubular shaft of each row's rake stirring rake, in each rake stirring rake, arrange gas circuit, the gas circuit of the rake stirring rake of each row is connected with a gas circuit of air-cored axis inside.The position of gas distribution interface and tubular shaft inlet mouth has been adjusted like this, the rotation along with tubular shaft can be realized, when the inlet mouth of gas distribution interface and tubular shaft is connected, gas enters inner and corresponding with the inlet mouth inner air path of air-cored axis (i.e. one of four gas circuits being divided into of cross partition), the gas orifice arranging rake stirring rake from be connected with this inner air path one again sprays, now just in time the rake stirring rake of this row moves to material concentrated area, to act on material, realize the gas of ejection while stirring to material concentrated area, along with the reach of material, carry out heat exchange until moisture in material simultaneously, formic acid is dried to reach specification of quality, product outlet place below dram end discharges the unlap of " spray of negative pressure baker " finished product potassium primary phosphate.
For convenience of the processing stage of observation material and the internal structure of maintenance dram, dram outer wall arranges spy hole (hole of convenient observation materiel machining degree) and manhole (hole of convenient for maintaining personnel turnover) respectively.
Adopt the air-cored axis different from transmission rotation axis as rotation axis, the power of rotation can either be provided for rake stirring rake, utilize air-cored axis's internal space difference four independently gas circuit simultaneously, and be connected with gas, the gas temperature used as required, carry out air inlet control, select to use (hygroscopic gas of use is inert nitrogen gas, carbonic acid gas, helium or argon gas, reaches explosive range to avoid oxygen) as air inlet through steam-heated rare gas element (general designation hygroscopic gas).Absorb steam, hygroscopic gas after formic acid gas is back to and synthesizes liquid with alkaline potassium formiate in absorptions, storage element and react, after sour gas to be absorbed, the hygroscopic gas after dewatering enters in spray of negative pressure baker again and recycles.
When air-cored axis's band rake type stirring rake rotates to material concentration zones, hygroscopic gas ejection forms boiling state to make the gentle body of material, the abundant heated material transpiring moisture of hot gas and formic acid, the moisture of evaporation and the hot gas of formic acid and cooling are together left " spray of negative pressure baker " by the vacuum port of top spray tower, complete the effect of material drying.Inner condition of high vacuum degree is needed when starting to spray, treat that bottom bank accumulated amount reaches requirement, stop spraying changing to spray into gas by air-cored axis and rake stirring rake and make the corresponding vacuum tightness of material fluidized drying decline even close to normal pressure to some extent, fluidized drying is to material moisture, formic acid content reaches qualified finished product requirement, start to open bottom discharge valve blowing, qualified material unlap is finished product, the product obtained after the process of spray of negative pressure baker as shown in Figure 1 has potassium primary phosphate, Potassium hydrogen diformate, potassium formiate, product calcium formiate is obtained after also selecting to add the process of spray of negative pressure baker after the reaction of material oxidation calcium.
Compared with prior art, in its industrial chain products production for reach material balance and formic acid and potassium formiate synthesize in the excessive factor of formic acid, potassium primary phosphate output is corresponding is greater than Potassium hydrogen diformate output.For equilibrium market sell produce Product Process can flexible industrial chain product production, or increase industrial chain other products output, in figure, other products production unit Technology is very general ripe, consume with the form of surface evaporation for all processing wastewaters in systems approach enter mineral hot furnace tail gas wet-dry change purification washing circulatory pool in figure, also can consume the processing wastewater that in garden, other products produces, the acid gas produced in all systems approaches absorbs neutralization by " alkaline potassium formiate synthesis liquid " and reduces its alkalescence, this cover system and method are process for cleanly preparing, low input, low cost, raw material mostly is the by product of environment protection treating or production capacity surplus, produce market Poly-generation industrial chain capacious:
A. 80% of dust to remove in dry method in mineral hot furnace tail gas, remaining is removed by wet method washing, water washing cycles pond is entered by dust after wet method washing, in pond, water flow velocity reduces dust settling and forms dirt mud (title coal slime), in wet method washing, recirculated water fully contacts washing with high-temperature furnace gas, heat in furnace gas is delivered in water and recirculated water is heated up, namely recirculated water evaporate (circulatory pool does not establish sewage draining exit) with the form of surface evaporation to aerial diffusion in circulatory pool, and the processing wastewater needing rear portion Chemical Manufacture to produce carrys out the water of supplementary surperficial vaporization losses.
B. the wet-dry change purification dust that produces of furnace gas and coal slime fully mix, the moisture in moisture coal slime is utilized to knock out kindling material in dust, transport dump again to mix with fire coal, enter coal firing boiler when burning, wherein calcium oxide does the sulfide in sweetening agent absorption fire coal, formed and be difficult to calcium sulfate, the calcium sulfite dissolved, the calcareous and organism of carbon dust, tar burn and produces heat in stove, and when burning, prussiate decomposes changes into harmless material.
C. emission gases after pressure swing adsorption decarbonization, be purer carbonic acid gas, carbon monoxide and join the potassium hydroxide solution reactive adsorption carbonic acid gas that alkali sends here and generate solution of potassium carbonate, absorption alkali lye reaches normality, power transmission solution Repone K workshop section refined brine, the gas after absorbing carbon dioxide mainly carbon monoxide return-air cabinet does source of the gas.
D. after synthesizing release of pressure, gas phase is mainly all the other dry gas of high-temperature water vapor is hydrogen, methane, nitrogen etc., high temperature gas phase is first removed the moisture in gas phase by water cooler to liquid caustic soda heating by alkali preheater again, the water that condensation, cooling obtain is for the make up water of wet-dry change purification washing circulatory pool, dry gas contain more than 50% hydrogen or effectively inflammable gas be greater than 60%, variable-pressure adsorption extracts hydrogen, hydrogen is used for the output of the synthesis increase PVC of hydrogenchloride in PVC production, carry the gas after hydrogen and still there is incendivity, or dry gas directly burns and asks for heat energy.
E. " alkaline potassium formiate synthesis liquid " can be sold as product by evaporating the liquid potassium formiate directly obtaining 75%, continues to be evaporated to 90% and produces for potassium primary phosphate and Potassium hydrogen diformate, or enters spray of negative pressure baker and obtain pressed powder potassium formate product.
F. the formic acid of potassium primary phosphate by-product: first for the production of Potassium hydrogen diformate products production, consider that market can be synthesized calcium formiate with calcium oxide, calcium hydroxide or calcium carbonate and be entered spray of negative pressure baker through solid-liquid separation solid and obtain pressed powder calcium formiate product, also concentrate can be processed into standard compliant formic acid product.
Accompanying drawing explanation
Fig. 1 is the method flow schematic diagram that the present invention produces potassium primary phosphate coproduction Potassium hydrogen diformate.
Fig. 2 is the structural representation (1, side, sectional) of the storage element that the present invention adopts, and wherein 1 is tank interior conduit, and 2 is injection pipe, and 3 is pipeline.
Fig. 3 is the structural representation (2, overlook and analyse and observe) of the storage element that the present invention adopts, and wherein 1 is tank interior conduit, and 2 is injection pipe.
Fig. 4 is the pipeline reactor structural representation (1, side-looking) that the present invention adopts.
Fig. 5 is the pipeline reactor structural representation (2, overlook and analyse and observe) that the present invention adopts.
Fig. 6 is the spray of negative pressure baker structural representation (1, diagrammatic side-view cross-sectional) that the present invention adopts.
Fig. 7 is the spray of negative pressure baker structural representation (2) (side-view by A-A direction in Fig. 6) that the present invention adopts.
Fig. 8 is gas distribution interface structural representation (sectional view) in the spray of negative pressure baker that adopts of the present invention.
Fig. 9 is rake stirring rake (leaf) structural representation in the spray of negative pressure baker that adopts of the present invention.
Figure 10 is the spray of negative pressure baker structural representation (3) (side-view by B-B direction in Fig. 6) that the present invention adopts.
Embodiment
Technical scheme of the present invention is further illustrated below in conjunction with specific embodiment.
As shown in accompanying drawing 2-3, the structural representation of the storage element that the present invention adopts, wherein 1 is tank interior conduit, and 2 is injection pipe, and 3 is pipeline.Storage element is that storage tank blending device is made up of burden storage tank and pump, tank interior conduit is set in burden storage tank, be connected with pump by pipeline at the bottom of the tank of burden storage tank, pump is connected with the tank interior conduit entrance of the tank deck of burden storage tank by another road pipeline, described tank interior conduit and burden storage tank height basically identical, from top to bottom evenly arrange the injection pipe be connected with tank interior conduit, the sectional area summation of described injection pipe is equivalent to tank interior conduit sectional area.Select to arrange opening for feed at the top of burden storage tank, such as charging A, charging B, enter burden storage tank to make the material refluxed in system and react.Injection pipe quantity is preferably 3-6, the outlet of injection pipe is 90-135 ° (i.e. the outlet of injection pipe and angles of top-down feedstock direction) with the angle a of the tank interior conduit vertically arranged, in injection pipe exit, liquid tangentially in downward direction sprays with concentrically ringed on burden storage tank cross section, to facilitate the mixture of whole material.Adopt spray regime to replace traditional mechanical stirring, adopt reflux type carry out the circulation of material and fully mix.
As shown in accompanying drawing 4-5, the pipeline reactor structural representation that the present invention adopts, the top of described pipeline reactor is adopted to realize circulating by pipeline and condenser, circulate to make formic acid and participate in reaction, the material participating in reaction enters from pipeline reactor lower end, and reacted material autoreaction material outlet flows out; Arrange four material feeding mouths at pipeline reactor lower end edge even circumferential, four the material feeding mouths being positioned at sustained height form one deck material feeding mouth.Described pipeline reactor adopts cylinder shape aspect ratio to be 2 ~ 50:1, upper and lower two ends adopt normal ellipsoidal head shutoff, and with heat exchange jacket, top with vapor condensation interchanger, phlegma can control the sealing load balance liquid seal apparatus refluxing and take out system of leaving.Material feeding pressure is 2 ~ 10 times of cylindrical reactor height (i.e. tubular reactor height) water column.Preferably 2-5 layers, described material feeding mouth; The described material feeding mouth being positioned at sustained height is consistent with horizontal direction angle, preferably 100-135 °; Be positioned at the tangential direction charging of material feeding mouth with tubular reactor circumference of sustained height, wherein phosphoric acid and melting potassium formiate are respectively from the material feeding mouth charging be positioned at angular direction, another two are positioned to the material feeding mouth of angular direction that (namely diagonal angle A, C or B, D import enter respectively for phosphoric acid and melting potassium formiate for the charging of vinasse, other two mouthfuls are entered vinasse, the vinasse of 21# as shown in Figure 1 after distillation).
As shown in accompanying drawing 6-10, the present invention adopt spray of negative pressure baker and baker, rake stirring rake structural representation.Described spray of negative pressure baker is made up of spray tower and baker.Described spray tower is cylinder shape aspect ratio is between the general diameter of 2 ~ 10:1 1 ~ 10 meter, feeder, rotating centrifugal distributor and vacuum port are set at spray tower top, described feeder selects feeding screw to be connected with pipeline, mass transport to be dried is entered in spray tower, through the effect of rotating centrifugal distributor, to make material be uniformly distributed, and vacuum port is utilized to carry out vacuumizing process.Crystal after described feeding screw import receives centrifugation adds material seal apparatus in course of conveying, has completely cut off moisture eliminator and extraneous gas intercommunication.
Rake type dryer selected by described baker, be made up of dram, Heat exchange jacekt, air-cored axis and agitating unit, described dram is drum, and be connected with the lower end of spray tower by being arranged on the interface in dram, the lower end of described dram arranges product outlet; Described Heat exchange jacekt parcel dram, arranges steam inlet in Heat exchange jacekt upper end, arranges condensation-water drain in Heat exchange jacekt lower end.In dram, coaxially air-cored axis is set, two ends and the dram sidewall of air-cored axis adopt mechanical seal or packing seal to be connected, compared with driving the turning axle of agitating unit in existing rake type dryer, at the center of whole air-cored axis, cross partition is set, cross partition is arranged along the axis of air-cored axis, four spaces do not communicated with each other to make the internal space of whole air-cored axis be split as, for transport gas; The outer wall being positioned at the air-cored axis of the outer side of dram sidewall along the circumferential direction arranges four inlet mouths, four gas circuits (space that namely cross partition four of being divided into are obstructed each other) of described four inlet mouths corresponding tubular shaft inside respectively, the tubular shaft of this side is ventilate in four spaces of air-cored axis's internal detachment; In air-cored axis, circumferentially agitating unit is set, described agitating unit adopts the rake stirring rake of rake baker (also known as vacuum rake type dryer), rake stirring rake arranges four rows along tubular shaft axial direction due, a gas circuit in the corresponding tubular shaft of each row's rake stirring rake, in each rake stirring rake, arrange gas circuit, the gas circuit of the rake stirring rake of each row is connected with a gas circuit of air-cored axis inside.The position of gas distribution interface and tubular shaft inlet mouth has been adjusted like this, the rotation along with tubular shaft can be realized, when the inlet mouth of gas distribution interface and tubular shaft is connected, gas enters inner and corresponding with the inlet mouth inner air path of air-cored axis (i.e. one of four gas circuits being divided into of cross partition), the gas orifice arranging rake stirring rake from be connected with this inner air path one again sprays, now just in time the rake stirring rake of this row moves to material concentration zones, to act on material, realize the gas of ejection while stirring to material concentrated area, along with the reach of material, carry out heat exchange until moisture in material simultaneously, formic acid is dried to reach specification of quality, product outlet place below dram end discharges the unlap of " spray of negative pressure baker " finished product product.
For convenience of the processing stage of observation material and the internal structure of maintenance dram, dram outer wall arranges spy hole (hole of convenient observation materiel machining degree, does not mark in figure) and manhole (hole of convenient for maintaining personnel turnover) respectively.
Adopt the air-cored axis different from transmission rotation axis as rotation axis, the power of rotation can either be provided for rake stirring rake, utilize air-cored axis's internal space difference four independently gas circuit simultaneously, and be connected with gas, the gas temperature used as required, carry out air inlet control, select to use as air inlet through steam-heated nitrogen or rare gas element (general designation hygroscopic gas).Absorb steam, hygroscopic gas after formic acid gas is back to and synthesize liquid with alkaline potassium formiate in storage element and react, after sour gas to be absorbed, reheat to enter in spray of negative pressure baker after dewatering and recycle.
When air-cored axis drives row's rake stirring rake to rotate to material concentration zones, hygroscopic gas ejection forms boiling state to make the gentle body of material, the abundant heated material transpiring moisture of hot gas and formic acid, the moisture of evaporation and the hot gas of formic acid and cooling are together left " spray of negative pressure baker " by the vacuum port of top spray tower, complete the effect of material drying.Inner condition of high vacuum degree is needed when starting to spray, treat that bottom bank accumulated amount reaches requirement, stop spraying changing to spray into gas by air-cored axis and rake stirring rake and make the corresponding vacuum tightness of material fluidized drying decline even close to normal pressure to some extent, fluidized drying reaches qualified finished product requirement to material moisture, formic acid content, start to open bottom high-volume valve blowing, qualified material unlap is finished product.
As shown in Figure 1, the present invention produces the method flow schematic diagram of potassium primary phosphate coproduction Potassium hydrogen diformate, raw material is mainly calcium carbide stove exhaust (main component is carbon monoxide), potassium hydroxide, phosphoric acid (85wt%), calcium oxide, and product is mainly potassium primary phosphate, Potassium hydrogen diformate, potassium formiate and calcium formiate; The mixed tank of 12# storage is storage element (structure described above); 19#, 32#, 36# are spray of negative pressure moisture eliminator (structure described above), can select in addition to arrange spray of negative pressure moisture eliminator (not marking in figure) after material oxidation calcium participates in reaction, after spray of negative pressure drying, obtain product calcium formiate after the reaction; 17#, 30# are crystallizer, and structure is consistent, and select with jacket heat-exchanger, top with the airtight crystallization apparatus of vapor condensation interchanger and whipping appts, material enters material, bottom discharge by top; 29#, 16# are pipeline reactor (structure described above); 18#, 31# are separator, and structure is consistent, select airtight separating centrifuge to increase adapter at its top; 21# is distiller, adopts to be with to stir, the still distillation device of jacket steam heating, negative pressure of vacuum operation in still, and gas phase is purified to condenser condenses through purification pot and obtains liquid formic acid for Potassium hydrogen diformate production.The mother liquor that 31# is separated directly stores up mixed tank and is connected with 12#, the hygroscopic gas obtained through 19# and 32# spray of negative pressure moisture eliminator enters " alkaline potassium formate solutions " absorption tower 51# and 50# respectively, and the liquid in the mixed tank 12# of utilization storage mixes in storage and circulates between tank and absorption tower after absorbing; Gas simultaneously after 23 condensations receive, is connected with " alkaline potassium formate solutions " absorption tower 50#, and the liquid in the mixed tank 12# of utilization storage mixes in storage and circulates between tank and absorption tower after absorbing.Select the basic chemical industry equipment such as pipeline, control valve, compressor, connect according to route shown in the drawings, and the pipeline reactor of said structure, storage element and spray of negative pressure moisture eliminator are connected among pipeline and can debug.
Embodiment 1
Starting material and output balance sheet
As shown in Figure 1: 1# ~ 4# after being purified by wet-dry change by installation 2.55 ten thousand KVA calcium carbide stove exhaust: atmospheric CO content is greater than 75%, oxygen is less than 0.5%, hydrogen about 15%, dust are less than 10mg/Nm
3, gas flow is 2000 ~ 2500Nm
3/ h enters gas holder and stores, and wherein wet-dry change purification washing circulatory pool 39# make up water is from the processing wastewater 48# at rear portion, and dust coal slime fully mixes 38# and is sent to coal firing boiler 43# and makes sweetening agent.
The potassium hydroxide solution of Selective ion mode film chlor-alkali by-product: content 32% potassium hydroxide, flow 10 ~ 15Nm
3/ h, be pressurized to by 8# and be less than 2.4MPa and enter preheater 9# (tubulation preheater), high temperature gas phase gas after adopting synthesis release of pressure to be separated heats supercharging liquid caustic soda, more than 165 DEG C are preheated to again again with the gas and vapor permeation being less than 2.4MPa through gas compressor 5# pressurized gas top hole pressure from gas holder, reacted by tubular type synthesis reactor 10# and generate " alkaline potassium formiate synthesis liquid ", technique is by DCS or Artificial Control synthetic reaction condition, in cyclonic separator 11#, gas-liquid is separated: gas phase enters 9# tubulation preheater and heats to liquid caustic soda by afterbody release of pressure, gas phase continues condensation, cooling 41# collects condenses water and makes make up water for wet-dry change purification washing circulatory pool 39#, synthesis tail gas after dehydration is dry gas: hydrogen content is more than 50%, flow 300 ~ 800Nm
3/ h.42# is gone to carry hydrogen explained hereafter hydrogen flowing quantity 200 ~ 500Nm
3/ h, content more than 99%, 11# is separated liquid phase " alkaline potassium formiate synthesis liquid ": potassium formiate content 400 ~ 800g/L, potassium hydroxide content 3 ~ 10g/L, flow are 7 ~ 16Nm
3/ h, enter the mixed tank 12# of storage and be incubated storage, after the receipt portion's Potassium hydrogen diformate produce in by-product acid aqueous mother liquor and absorb " alkaline potassium formiate synthesis liquid " after acid gas absorption by pump delivery to " spray of negative pressure baker " system in absorption tower and return the mixed tank of storage, the mixed tank mixture recycle pump mixture " alkaline potassium formiate synthesis liquid " of start by set date storage, is down to 1 ~ 5g/L standby evaporation 13# workshop section evaporation and 35# when potassium hydroxide content and is concentrated to 37# and obtains solid phase prod potassium formiate or sample examination reaches liquid product concentration and enters 34# and carry out liquid product potassium formiate packaging in 13#.
By pump delivery " alkaline potassium formiate synthesis liquid " to outer circulation double-effect evaporator 13#, evaporated by steam heating, heating steam condensation water collection in evaporative process, send boiler back to and continue heat absorption generation steam, condensate water circulatory uses, collected by the steam condensate of evaporation material and send wet-dry change to purify washing circulatory pool 39# to make make up water, " alkaline potassium formiate synthesis liquid " be evaporated to the melting potassium formiate 14# of content between 85 ~ 90%, temperature between 100 ~ 170 DEG C, flow 5 ~ 10Nm
3/ h is delivered to rear portion respectively by high-temperature pump or potential difference and produces.
Content 90% melting potassium formiate 14# quality of regulation flow is sent here at 3 ~ 6Nm by high-temperature pump
3/ h and 15# pumping carrys out the phosphoric acid quality of regulation flow of 85% content at 2 ~ 4Nm
3/ h, enters 16# pipeline reactor respectively, the end enter on the successive reaction that goes out, the material reacting qualified enters 17# crystallizer by top: every platform volume 10 ~ 35Nm
3totally 10 ~ 15, canful was through the insulation of 10 ~ 30 hours, decrease temperature crystalline process also adds crystal seed, form regular potassium primary phosphate crystallization suspension, enter the airtight separation of 18# centrifuge separator: crystal enters 19# spray of negative pressure baker and obtains product potassium primary phosphate, output 2 ~ 6T/h, potassium primary phosphate quality reaches the standard of HG2321-92, centrifugation mother liquor goes 21# to distill, distillation gas phase enters 22# cleaner and enters 23# condenser again, obtain phlegma content 50 ~ 75%, the formic acid of flow 0.8 ~ 2T/h, send Potassium hydrogen diformate production process, obtain raffinate at the bottom of still after distillation and return 16# pipeline reactor.
Content 90% melting potassium formiate 14# difference quality of regulation flow is sent here at 3 ~ 6Nm by high-temperature pump
3/ h, obtains the formic acid adjust flux 0.8 ~ 2T/h of content 50 ~ 75% with distillation 23# condenser, enters 29# pipeline reactor respectively, the end enter on the successive reaction that goes out, the material reacting qualified flows into 30# crystallizer by upper outlet, every platform crystallizer volumes, 15 ~ 25Nm
3totally 10 ~ 15, canful is through the decrease temperature crystalline process of 10 ~ 30 hours and the crystal seed added, form regular Potassium hydrogen diformate crystallization suspension, enter airtight 31# centrifuge separator to be separated: crystal enters 32# spray of negative pressure baker and obtains product Potassium hydrogen diformate, output 3 ~ 6T/h, Potassium hydrogen diformate content reaches more than 98% standard, airtight centrifugation mother liquor goes 12# to store up mixed tank neutralization " alkaline potassium formiate synthesis liquid ", 19#, 32# spray of negative pressure baker vacuumizes and drying section hygroscopic gas removes 50# with vacuum pipe, " alkaline potassium formiate synthesis liquid " cyclic absorption sour gas is beaten by pump 49# in 51# absorption tower, for insurance is directly absorbed by 52# alkali lye again, final gas enters 53# vacuum pump, as spray of negative pressure baker drying section hygroscopic gas adopts rare gas element can be recycled.
Process system controls evaporating, emitting, dripping or leaking of liquid or gas, and on the basis ensureing quality product, reduce consumption, reduction production cost that namely internal circulating load reduces general facilities, Poly-generation industrial chain is more tending towards economy, cleaner production.
Embodiment 2:
Content 90% melting potassium formiate 1000g is got in above-described embodiment 1 " alkaline potassium formiate synthesis liquid " evaporative process, put into 3000mml band to stir, in the stainless steel storage tank 14# of insulation and electric heating cover, add the pressure that rare gas element or electrically heated make with 0.1MPa in tank, by through four tangential entries in valve pipe connecting tube reactor 16# bottom one of lower outlet, pipeline reactor: select the stainless steel tube of internal diameter ф 20 wall thickness 2.5mm high 1.5 meters, at 1 meter of absolute altitude place outlet, this 1 meter high with electrically heated and muff, 0.5 meter, top adds chuck water flowing heat exchange, pipeline reactor bottom corresponding another import access link through valve pipe with the stainless steel storage tank lower part outlet of 15#3000ml, 15# storage tank is equipped with 1235g content 85% phosphoric acid, the pressure that rare gas element or electrically heated make with 0.1MPa in tank is added to phosphoric acid storage tank, enter by mass flow ratio in 16# pipeline reactor (having front primary first-order equation clout to be heated to molten state temperature in pipeline reactor identical with the melting potassium formiate) process that feeds intake at lower part outlet regulated valve pipeline and melting potassium formiate simultaneously and terminate to make to keep phosphoric acid excessive eventually.
Simultaneously the raffinate input with pressure of last time distillation in the process that feeds intake, the qualified material of reaction is discharged in pipeline reactor 1 meter of outlet simultaneously, the crystallizer that the Stainless Steel Band entering 17#3000mml by pipeline fluid-tight stirs, receiving enough reaction masses enters in crystallizer, after continuing the insulated and stirred making to keep 1-2 hour in crystallizer, cooling regulates temperature of charge to obtain the suspension containing regular potassium primary phosphate xln with input crystal seed again, put into 18# centrifuge separator (or Suction filtration device suction filtration) to be separated: filter cake enters 19# spray of negative pressure moisture eliminator, spray of negative pressure moisture eliminator: spraying section diameter 1.2 meters high 3 meters, drying section diameter 0.8 meter is long 2.5 meters, jacket temperature controls lower than 200 DEG C, rake colter jet temperature controls lower than 200 DEG C, vacuum tightness 0.07 ~ 0.09MPa is controlled during spraying dry, control stirring during oven dry and spray into amount of inert gas at 2-5Nm
3/ h, sample examination moisture content, formic acid content are qualified, obtain product potassium primary phosphate 1450g content 98%, and spray of negative pressure moisture eliminator vacuum tail gas is purified absorption by 51# " alkaline potassium formiate synthesis liquid ".Centrifuge separator 18#: the four-hole bottle that separation mother liquor puts into 3000mml adds thermal distillation, gas phase is collected enter in storage tank 23# through purification, condensation, cooling, obtain the formic acid 720g of content 63.4%, after distillation, raffinate 250g gets time use ready, potassium primary phosphate yield 97.5%, carboxylic acid Yield 92.6%.
Content 90% melting potassium formiate 965g is got in above-described embodiment 1 " alkaline potassium formiate synthesis liquid " evaporative process, put into 3000mml band to stir, in the stainless steel storage tank 14# of insulation and electric heating cover, add the pressure that rare gas element or electrically heated make with 0.1MPa in still, by through four tangential entries in valve pipe connecting tube reactor 29# bottom one of lower outlet, pipeline reactor: select the stainless steel tube of internal diameter ф 20 wall thickness 2.5mm high 1.5 meters, at 1 meter of absolute altitude place outlet, this 1 meter high with electrically heated and muff, 0.5 meter, top adds chuck water flowing heat exchange, pipeline reactor bottom corresponding another import access link through valve pipe with the stainless steel storage tank 23# lower part outlet of 3000ml, 23# stainless steel storage tank is equipped with the formic acid 720g of content 63.4%, to storage tank add rare gas element or electrically heated make pressure reach 0.1MPa lower part outlet regulated valve pipeline and melting potassium formiate simultaneously in mass ratio example enter in pipeline reactor (having front primary first-order equation clout to be heated to molten state temperature in pipeline reactor identical with the melting potassium formiate) process that feeds intake and terminate to make keep formic acid excessive end.
A part of mother liquor input with pressure after simultaneously the last time being separated in the process that feeds intake, the qualified material of reaction is discharged in pipe reaction still 1 meter of outlet simultaneously, the band being entered 3000mml by pipeline fluid-tight stirs in the crystallizer 30# of stainless steel jacket for heat exchange, receive the crystallizer of enough reaction masses, after continuing the insulated and stirred making to keep 0.5-2 hour in crystallizer, cooling regulates temperature of charge to obtain the suspension containing regular Potassium hydrogen diformate xln with input crystal seed again, put into separating centrifuge 31# (or Suction filtration device suction filtration) to be separated: filter cake enters spray of negative pressure moisture eliminator 32#, spray of negative pressure moisture eliminator: spraying section diameter 1.2 meters high 3 meters, drying section diameter 0.8 meter is long 2.5 meters, jacket temperature controls lower than 100 DEG C, rake stirring rake jet temperature controls lower than 100 DEG C, vacuum tightness 0.07 ~ 0.09MPa is controlled during spraying dry, control stirring during oven dry and spray into amount of inert gas at 2-5Nm
3/ h, sample examination formic acid, moisture content are qualified, obtain product Potassium hydrogen diformate 1150g content 98%, and the dry vacuum tail gas of spray of negative pressure is purified absorption by 50# " alkaline potassium formiate synthesis liquid ".Centrifuge separator 31#: separation mother liquor major part returns the mixed tank of " alkaline potassium formiate synthesis liquid " storage, small portion returns pipeline reactor, Potassium hydrogen diformate yield 83.8%.
Embodiment 3:
Content 85% melting potassium formiate 1000g is got in above-described embodiment 1 " alkaline potassium formiate synthesis liquid " evaporative process, get the system and method for 1200 content 85% phosphoric acid employings with embodiment 2, obtain finished product potassium primary phosphate 1380g content 98%, and be separated the formic acid 710g that mother liquor distills, vapor condensation obtains content 61%, after distillation, raffinate 200g gets time use ready, potassium primary phosphate yield 96.2%, carboxylic acid Yield 93.0%.
Content 85% melting potassium formiate 900g is got in above-described embodiment 1 " alkaline potassium formiate synthesis liquid " evaporative process, above-mentioned condensation is obtained the system and method for formic acid 710g employing with embodiment 2 of content 61%, obtain finished product Potassium hydrogen diformate 980g content 98%, separation mother liquor major part returns the mixed tank of " alkaline potassium formiate synthesis liquid " storage, small portion returns pipeline reactor, Potassium hydrogen diformate yield 81.1%.
Embodiment 4:
Content 85% melting potassium formiate 1000g is got in above-described embodiment 1 " alkaline potassium formiate synthesis liquid " evaporative process, get the system and method for 1330g content 75% monophosphate monophosphate employing with embodiment 2, obtain finished product potassium primary phosphate 1400g content 96%, and be separated the formic acid 850g that mother liquor distills, vapor condensation obtains content 51%, after distillation, raffinate 250g gets time use ready, potassium primary phosphate yield 97.6%, carboxylic acid Yield 93.1%.
Content 85% melting potassium formiate 700g is got in above-described embodiment 1 " alkaline potassium formiate synthesis liquid " evaporative process, above-mentioned condensation is obtained the formic acid 850g of content 51%, adopt the system and method with embodiment 2, obtain finished product Potassium hydrogen diformate 710g content 98%, separation mother liquor major part returns the mixed tank of " alkaline potassium formiate synthesis liquid " storage, small portion returns pipeline reactor, Potassium hydrogen diformate yield 75.6%.
Above to invention has been exemplary description; should be noted that; when not departing from core of the present invention, any simple distortion, amendment or other those skilled in the art can not spend the equivalent replacement of creative work all to fall into protection scope of the present invention.
Claims (9)
1. produce the method for potassium primary phosphate coproduction Potassium hydrogen diformate, it is characterized in that, comprise the steps:
Step 1, utilizes mineral hot furnace tail gas to purify, to make the volume fraction of carbon monoxide in tail gas more than 70%;
Step 2, the aqueous solution of the gas of carbon monoxide volume fraction step 1 obtained more than 70% and potassium hydroxide carries out reaction and generates alkaline potassium formiate and synthesize liquid, and it is excessive to control potassium hydroxide, to guarantee that carbon monoxide all participates in the synthesis of alkaline potassium formiate synthesis liquid; In described step 2, employing chlor-alkali industry electrolytic chlorination potassium byproduct weight percentage composition reacts at the potassium hydroxide aqueous solution of 32%, and is precisely controlled by DCS, to make reacted potassium hydroxide content between 3 ~ 10g/L; In step 2, the alkaline potassium formiate synthesis liquid of final synthesis enters in storage element;
Described storage element is that storage tank blending device is made up of burden storage tank and pump, tank interior conduit is set in burden storage tank, be connected with pump by pipeline at the bottom of the tank of burden storage tank, pump is connected with the tank interior conduit entrance of burden storage tank tank deck by another road pipeline, described tank interior conduit and burden storage tank height basically identical, the injection pipe be connected with tank interior conduit is from top to bottom evenly set, the sectional area summation of described injection pipe is equivalent to tank interior conduit sectional area, the outlet of injection pipe is 90 ~ 135 ° with the angle of the tank interior conduit vertically arranged, in injection pipe exit, liquid sprays downwards with tangential direction concentrically ringed on burden storage tank cross section, to facilitate the mixture accelerating whole material,
Step 3, potassium hydroxide excessive in alkaline potassium formiate synthesis liquid produced by Potassium hydrogen diformate formic acid gas that the acid mother liquid that produces and spray of negative pressure baker produce carry out in and, detect in the alkaline potassium formiate synthesis liquid of storage element: potassium formiate content is more than 400-800g/L, potassium hydroxide content is down between 1 ~ 5g/L, the alkaline potassium formiate synthesis liquid of storage element is evaporated, the potassium formiate of the molten state of weight percentage more than 90% can be obtained, the normal temperature phosphoric acid of the potassium formiate of described molten state and mass percentage 85% is utilized to enter the first pipeline reactor reaction to obtain potassium primary phosphate respectively by pump, material after reacting completely enters the first crystallizer, forms regular potassium primary phosphate xln, after being separated by the first separator: crystal enters the first spray of negative pressure baker and obtains product potassium primary phosphate, mother liquor is after distillation, vapor condensation obtains the formic acid of mass percentage 50 ~ 70%, the raffinate obtained at the bottom of still kettle is back in pipeline reactor, and wherein the gas phase of the first spray of negative pressure baker enters the first absorption tower, and alkaline potassium formate solutions circulates between the first absorption tower and storage element, mother liquor is after distillation, and vapor condensation obtains the formic acid of mass percentage 50 ~ 70% after purification, condensation receive, and is connected respectively with second pipe reactor with second absorption tower,
Step 4, the potassium formiate of the molten state of the weight percentage more than 90% that step 3 obtains and the formic acid of mass percentage 50 ~ 70% enter second pipe reactor reaction to obtain Potassium hydrogen diformate respectively by pump, the material reacted completely enters the second crystallizer crystallization, form regular Potassium hydrogen diformate xln, be separated by the second separator: be separated mother liquor and go to be provided with in the storage element of alkaline potassium formiate synthesis liquid and alkaline potassium formiate synthesis liquid; Xln enters the second spray of negative pressure baker and obtains product Potassium hydrogen diformate, and gas phase enters second absorption tower, and alkaline potassium formate solutions circulates between second absorption tower and storage element;
In described step 3 and 4, the the first and second pipeline reactor structures used are consistent, the top of described pipeline reactor is adopted to realize circulating by pipeline and condenser, circulate to make formic acid and participate in reaction, the material participating in reaction enters from pipeline reactor lower end, and reacted material autoreaction material outlet flows out; Arrange four material feeding mouths at pipeline reactor lower end edge even circumferential, four the material feeding mouths being positioned at sustained height form one deck material feeding mouth; The described material feeding mouth being positioned at sustained height is consistent with horizontal direction angle; Be positioned at the tangential direction charging of material feeding mouth with tubular reactor circumference of sustained height, wherein phosphoric acid and melting potassium formiate are respectively from the material feeding mouth charging be positioned at angular direction, and another two are positioned at the charging for vinasse of the material feeding mouth of angular direction; Described pipeline reactor adopts cylinder shape aspect ratio to be 2 ~ 50:1, upper and lower two ends adopt normal ellipsoidal head shutoff, and with heat exchange jacket, top with vapor condensation interchanger, phlegma can control the sealing load balance liquid seal apparatus refluxing and take out system of leaving; Material feeding pressure is 2 ~ 10 times of cylindrical reactor height (i.e. tubular reactor height) water column;
In described step 3 and 4, the the first and second spray of negative pressure baker structures used are consistent, described spray of negative pressure baker is made up of spray tower and baker, described spray tower is cylinder shape aspect ratio is between the general diameter of 2 ~ 10:1 1 ~ 10 meter, at spray tower top, feeder is set, rotating centrifugal distributor and vacuum port, described feeder is connected with pipeline, and select feeding screw to enter in spray tower by mass transport to be dried, through the effect of rotating centrifugal distributor, be uniformly distributed to make material, and utilize vacuum port to carry out vacuumizing process, crystal after described feeding screw import receives centrifugation adds material seal apparatus in course of conveying, spray of negative pressure moisture eliminator and extraneous gas intercommunication are completely cut off,
Existing rake type dryer selected by described baker, be made up of dram, Heat exchange jacekt, air-cored axis and agitating unit, described dram is drum, and be connected with the lower end of spray tower by being arranged on the interface in dram, the lower end of described dram arranges product outlet; Described Heat exchange jacekt parcel dram, arranges steam inlet in Heat exchange jacekt upper end, arranges condensation-water drain in Heat exchange jacekt lower end; In dram, concentric shafts arranges air-cored axis, two ends and the dram sidewall of air-cored axis are fixedly linked, compared with driving the turning axle of agitating unit in existing rake type dryer, at the center of whole air-cored axis, cross partition is set, cross partition is arranged along the axis of air-cored axis, with four spaces making the internal space of whole air-cored axis be split as not communicate with each other (space that namely cross partition four of being divided into are obstructed each other), for transport gas; The outer wall being positioned at the air-cored axis of the outer side of dram sidewall along the circumferential direction arranges four inlet mouths, four gas circuits of described four inlet mouths corresponding tubular shaft inside respectively, the tubular shaft of this side is four spaces ventilations of air-cored axis's internal detachment; In air-cored axis, circumferentially agitating unit is set, described agitating unit adopts the rake stirring rake of rake baker, rake stirring rake arranges four rows along tubular shaft axial direction due, a gas circuit in the corresponding tubular shaft of each row's rake stirring rake, in each rake stirring rake, arrange gas circuit, the gas circuit of the rake stirring rake of each row is connected with a gas circuit of air-cored axis inside.The position of gas distribution interface and tubular shaft inlet mouth has been adjusted like this, the rotation along with tubular shaft can be realized, when the inlet mouth of gas distribution interface and tubular shaft is connected, gas enters inner and corresponding with the inlet mouth inner air path of air-cored axis (i.e. one of four gas circuits being divided into of cross partition), the gas orifice arranging rake stirring rake from be connected with this inner air path one again sprays, now just in time the rake stirring rake of this row moves to material concentrated area, to act on material, realize the gas of ejection while stirring to material concentrated area, along with the reach of material, carry out heat exchange until moisture in material simultaneously, formic acid is dried to reach specification of quality, product outlet place below dram end discharges " spray of negative pressure baker " finished product unlap.
2. the method for production potassium primary phosphate coproduction Potassium hydrogen diformate according to claim 1, it is characterized in that, in described step 1, the method of dry cleaning and/or wet purification is adopted to process mineral hot furnace tail gas, to control the volume fraction of carbon monoxide in tail gas, reduce the content of other compositions to minimum simultaneously; After the precipitation obtained in dry cleaning and/or wet purification process, dust, coal slime mix, mix the sweetening agent being used as coal firing boiler with fire coal.
3. the method for production potassium primary phosphate coproduction Potassium hydrogen diformate according to claim 1, it is characterized in that, in described step 2, the injection pipe quantity be connected with tank interior conduit is from top to bottom evenly set and is 3-6, reflux type is adopted to carry out the circulation of material and fully mix, alkalescence potassium formiate synthesis liquid circulates in storage element, simultaneously in and the acidic substance that formed in subsequent step.
4. the method for production potassium primary phosphate coproduction Potassium hydrogen diformate according to claim 1, is characterized in that, in described step 3, the potassium formiate temperature of described melting molten state is 120-160 DEG C; In described step 3, the alkaline potassium formiate synthesis liquid of storage element is carried out evaporating to obtain liquid potassium formiate; In described step 3, the potassium formiate evaporating the molten state of the weight percentage more than 90% obtained enters spray of negative pressure moisture eliminator and processes, to obtain potassium formate product after dissolving is concentrated.
5. the method for production potassium primary phosphate coproduction Potassium hydrogen diformate according to claim 1, it is characterized in that, in described step 3, mother liquor is after distillation, vapor condensation obtains the formic acid of mass percentage 50 ~ 70% after purification, condensation receive, by concentrated, to obtain product formic acid, then be obtained by reacting product calcium formiate with calcium oxide.
6. the method for production potassium primary phosphate coproduction Potassium hydrogen diformate according to claim 1, it is characterized in that, in step 3 and 4, the first and second mold structures used are consistent, select with jacket heat-exchanger, top with the airtight crystallization apparatus of vapor condensation interchanger and whipping appts, material enters material, bottom discharge by top; In step 3 and 4, the first and second cyclone separator arrangements of use are consistent, select airtight separating centrifuge to increase adapter and valve at its top; In step 3, the distillation plant of use adopts band to stir, the still distillation device of jacket steam heating, negative pressure of vacuum operation in still.
7. the method for production potassium primary phosphate coproduction Potassium hydrogen diformate according to claim 1, it is characterized in that, in described step 3 and 4, in described pipeline reactor structure, preferably 2-5 layers, described material feeding mouth, the material feeding mouth and the horizontal direction angle that are positioned at sustained height are 10-45 °.
8. the method for production potassium primary phosphate coproduction Potassium hydrogen diformate according to claim 1, is characterized in that, in described step 3 and 4, in the structure of the spray of negative pressure baker of use, dram outer wall arranges spy hole and manhole respectively.
9. the method for production potassium primary phosphate coproduction Potassium hydrogen diformate according to claim 1, it is characterized in that, in described step 3 and 4, in the structure of the spray of negative pressure baker used, select through steam-heated rare gas element as hygroscopic gas, air inlet uses, described rare gas element is nitrogen, carbonic acid gas, helium or argon gas, absorb steam, hygroscopic gas after formic acid gas is back to absorption, synthesize liquid with alkaline potassium formiate in storage element to react, after sour gas to be absorbed, hygroscopic gas after dehydration enters in spray of negative pressure baker again and recycles.
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| CN201410197921.1A CN105084335B (en) | 2014-05-12 | 2014-05-12 | Cogeneration method for producing monopotassium phosphate and potassium diformate |
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| CN107778164A (en) * | 2016-08-30 | 2018-03-09 | 思科福（北京）生物科技有限公司 | A kind of preparation method of potassium diformate |
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