CN103991851A - New process for green and cyclic production of hydrazine hydrate - Google Patents
New process for green and cyclic production of hydrazine hydrate Download PDFInfo
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- CN103991851A CN103991851A CN201310064822.1A CN201310064822A CN103991851A CN 103991851 A CN103991851 A CN 103991851A CN 201310064822 A CN201310064822 A CN 201310064822A CN 103991851 A CN103991851 A CN 103991851A
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- hydrazine hydrate
- causticization
- urea
- sodium
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 title claims abstract description 132
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 18
- 125000004122 cyclic group Chemical group 0.000 title abstract 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 240
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 108
- 239000007788 liquid Substances 0.000 claims abstract description 95
- 235000011121 sodium hydroxide Nutrition 0.000 claims abstract description 80
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 claims abstract description 70
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 claims abstract description 66
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 54
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 53
- 239000007787 solid Substances 0.000 claims abstract description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 36
- 229910000019 calcium carbonate Inorganic materials 0.000 claims abstract description 33
- 239000011780 sodium chloride Substances 0.000 claims abstract description 30
- 239000000920 calcium hydroxide Substances 0.000 claims abstract description 29
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims abstract description 28
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims abstract description 28
- 238000000926 separation method Methods 0.000 claims abstract description 20
- 238000001704 evaporation Methods 0.000 claims abstract description 19
- 230000008020 evaporation Effects 0.000 claims abstract description 19
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 16
- 239000006227 byproduct Substances 0.000 claims abstract description 11
- 238000001914 filtration Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 67
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 26
- 230000036571 hydration Effects 0.000 claims description 15
- 238000006703 hydration reaction Methods 0.000 claims description 15
- 238000012805 post-processing Methods 0.000 claims description 15
- 238000009993 causticizing Methods 0.000 abstract description 29
- 238000003786 synthesis reaction Methods 0.000 abstract description 9
- 239000000460 chlorine Substances 0.000 description 116
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 99
- 239000004202 carbamide Substances 0.000 description 99
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 80
- 229910052801 chlorine Inorganic materials 0.000 description 80
- 235000017550 sodium carbonate Nutrition 0.000 description 52
- 229940001593 sodium carbonate Drugs 0.000 description 51
- 235000008733 Citrus aurantifolia Nutrition 0.000 description 40
- 235000011941 Tilia x europaea Nutrition 0.000 description 40
- 239000004571 lime Substances 0.000 description 40
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 39
- 238000002360 preparation method Methods 0.000 description 38
- 239000007844 bleaching agent Substances 0.000 description 30
- 235000011116 calcium hydroxide Nutrition 0.000 description 27
- ODINCKMPIJJUCX-UHFFFAOYSA-N Calcium oxide Chemical compound [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 26
- 239000000843 powder Substances 0.000 description 26
- 238000004062 sedimentation Methods 0.000 description 24
- 239000000292 calcium oxide Substances 0.000 description 23
- 235000012255 calcium oxide Nutrition 0.000 description 23
- 238000002474 experimental method Methods 0.000 description 23
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 20
- 239000011734 sodium Substances 0.000 description 19
- 239000003513 alkali Substances 0.000 description 16
- 239000002002 slurry Substances 0.000 description 15
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 13
- 239000004568 cement Substances 0.000 description 13
- 239000012452 mother liquor Substances 0.000 description 13
- 229910052708 sodium Inorganic materials 0.000 description 13
- 230000008014 freezing Effects 0.000 description 12
- 238000007710 freezing Methods 0.000 description 12
- XYQRXRFVKUPBQN-UHFFFAOYSA-L Sodium carbonate decahydrate Chemical compound O.O.O.O.O.O.O.O.O.O.[Na+].[Na+].[O-]C([O-])=O XYQRXRFVKUPBQN-UHFFFAOYSA-L 0.000 description 10
- 229940018038 sodium carbonate decahydrate Drugs 0.000 description 10
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 9
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 9
- 239000007858 starting material Substances 0.000 description 9
- 239000002699 waste material Substances 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000009413 insulation Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- ZPSXMXBYOFNZCN-UHFFFAOYSA-N sodium urea hypochlorite Chemical compound Cl[O-].[Na+].NC(=O)N ZPSXMXBYOFNZCN-UHFFFAOYSA-N 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 239000011575 calcium Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 238000003672 processing method Methods 0.000 description 3
- ULUZGMIUTMRARO-UHFFFAOYSA-N (carbamoylamino)urea Chemical compound NC(=O)NNC(N)=O ULUZGMIUTMRARO-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- PFLUPZGCTVGDLV-UHFFFAOYSA-N acetone azine Chemical compound CC(C)=NN=C(C)C PFLUPZGCTVGDLV-UHFFFAOYSA-N 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 238000005352 clarification Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- -1 consume 1.5 tons Chemical compound 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 238000003303 reheating Methods 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- NCGSLDXVMRCQPG-UHFFFAOYSA-K trisodium;carbonate;chloride Chemical compound [Na+].[Na+].[Na+].[Cl-].[O-]C([O-])=O NCGSLDXVMRCQPG-UHFFFAOYSA-K 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention relates to a new process for green and cyclic production of hydrazine hydrate. The process is characterized by: causticizing sodium carbonate as a by-product of hydrazine hydrate synthesis reaction into calcium carbonate and sodium hydroxide by calcium hydroxide, clarifying and filtering a causticized solution containing low-concentration hydrazine hydrate to remove solid calcium carbonate to obtain a causticization clear solution mainly containing sodium chloride, caustic soda, hydrazine hydrate and water, and then subjecting the causticization clear solution to evaporation, rectification, solid-liquid separation and other after-treatment units, thus obtaining commodity hydrazine hydrate with a hydrazine content of 80%, sodium chloride solids cyclically applicable to electrolysis, and a caustic soda solution cyclically applicable to hydrazine hydrate synthesis reaction.
Description
One, technical field:
The present invention relates to a kind of hydrazine hydrate green circulatory new process of production, belong to chemical technique technical field.
Two, background technology:
Hydrazine hydrate is a kind of important industrial chemicals, is widely used in medicine, agricultural chemicals, plastic, rubber whipping agent ADC production.Present stage, main ripe hydrazine hydrate production technique had ketazine technique and urea sodium hypochlorite oxidization technique (being called for short Wyler's process technique), the hydrazine hydrate quality product of ketazine explained hereafter is poor, its purification technique is abroad blocked, and the problem of this technique maximum is that the light salt brine that product per ton is 5% left and right by 40 tons of salts contgs of by-product cannot carry out effective environmental protection treatment; Urea sodium hypochlorite oxidization technique comparative maturity, good quality of product, is the main technique method of current domestic production hydrazine hydrate and whipping agent ADC.The commodity hydrazine hydrate that one ton of hydrazine content of the every production of urea sodium hypochlorite oxidization hydrazine hydrate production technique is 80% will consume 4.5 tons, hundred caustic soda of folding, consume 1.9 tons, chlorine, consume 1.5 tons, urea, 7 tons of saline and alkaline mud that contain sodium-chlor and sodium carbonate of this technique by-product, present stage is that the initial synthetic liquid that contains 4% left and right hydrazine hydrate is carried out freezing, 50% sodium carbonate in initial synthetic liquid is transformed into Sodium carbonate decahydrate crystal then through centrifuging, filter obtain solid Sodium carbonate decahydrate through reheating evaporation, oven dry obtains the soda ash that quality is lower; Filtrated stock is through evaporation concentration, and hydrazine hydrate and water vapor azeotropic steam and obtain hydrazine content through rectifying concentrate is 80% commodity hydrazine hydrate; The saline and alkaline mud of mixing that contains sodium-chlor and remaining sodium carbonate in evaporation concentration raffinate, mixes saline and alkaline mud and filters through extraction, filtrated stock circulation; The filter residue that filtration the obtains separation of need to re-refining obtains sodium-chlor and the sodium carbonate that purity is lower, and the lower sodium carbonate of the purity obtaining is carried out to causticization caustic soda processed, this process also reclaims the difficult saline and alkaline hydrazine waste liquor of lower concentration by producing simultaneously, and this waste liquor is directly to environmental emission.ErADC whipping agent manufacturer be by hydrazine hydrate initially synthetic liquid freezing and crystallizing remove portion Sodium carbonate decahydrate containing hydrazine mother liquor, directly add sulfuric acid or hydrochloric acid neutralization, after neutralization, directly in lower concentration hydration hydrazine solution, add excessive urea, then being warming up to 106 ℃ of left and right makes urea and hydrazine hydrate carry out condensation to become the biurea that is insoluble in water, biurea is filtered to a large amount of sodium-chlor that contains of rear remainder, the waste liquor of sodium sulfate and ammonia nitrogen is directly to environmental emission, one ton of ADC whipping agent product of every production will discharge 20 tons of waste liquors, and (wherein sodium-chlor is approximately 1.4 tons, approximately 1.2 tons, sodium sulfate, in 0.4 ton of the TAN of ammonia).In a word: in existing hydrazine hydrate production technological process, caustic soda consumption is high, the by product sodium-chlor reclaiming and sodium carbonate purity is low, purposes is limited, recovery value is low, fundamentally do not solve waste liquor discharge pollution on the environment, hydrazine hydrate production total cost is high.
Three, summary of the invention:
First object of the present invention is to provide a kind of method that reduces the caustic soda consumption of urea oxidation style hydrazine hydrate production technique, second object of the present invention is to provide a kind of low method of saline and alkaline by product recycle value that purity that solves by product sodium-chlor and sodium carbonate mixed crystal Separation and Recovery is low and reclaim, and the 3rd object of the present invention is the waste liquor discharge pollution on the environment thoroughly solving in hydrazine hydrate production process.
The present invention has used the sodium carbonate of calcium hydroxide and hydrazine hydrate building-up reactions by-product first to carry out causticizing reaction, hydrazine hydrate mixed solution after causticization is obtained to calcium carbonate solid through precipitation, filtration, washing, and calcium carbonate solid can deep processing become commodity light calcium carbonate or cement; Clarification, filter the causticization clear liquid obtain and mainly contain sodium-chlor, caustic soda, hydrazine hydrate, by causticization clear liquid evaporate again, the post-processing unit such as rectifying, solid-liquid separation: it is 80% commodity hydrazine hydrate that the hydrazine hydrate steam being evaporated obtains hydrazine content through rectifying; The sodium chloride crystal that evaporation concentration raffinate is separated out obtains caustic soda mother liquor and sodium-chlor crude product after filtration together with the continuous extraction of saline and alkaline slurry that contains caustic soda, hydrazine hydrate; Part caustic soda mother liquor returns to vapo(u)rization system, the continuous extraction of part caustic soda mother liquor makes hydrazine hydrate content wherein drop to 2g/l through evaporation concentration again and can be used as below caustic soda raw material, again generate clorox with chlorine reaction and turn back in the building-up reactions of hydrazine hydrate, the caustic soda using during hydrazine hydrate building-up reactions so has just formed closed cycle; The solid sodium chloride crude product that filtration is obtained just obtains with a small amount of clear water washing the solid sodium chloride that ammonia-nitrogen content is extremely low again, solid sodium chloride is dissolved into saturated solution, and be used as the raw material salt solution of electrolysis to the potroom that flows to chlor-alkali system after this saturated solution passes into chlorine oxidation denitrogenation, thereby formed the closed cycle of sodium-chlor.This technique has realized recycling of caustic soda, sodium-chlor, mixed crystal separation is become to monocrystalline separation, solved the difficult problem that saline and alkaline mud mixed crystal is difficult to separated and waste liquor exhaust emission environment, the recovery utilization rate of sodium-chlor, sodium carbonate is brought up to more than 95% from 40%～60%, the purity and the utility value that reclaim by product significantly improve, and the present invention is thoroughly changed high pollution, high material-consumption, the expensive shortcoming of urea sodium hypochlorite oxidization hydrazine hydrate production technique.
The object of the present invention is achieved like this:
(1) the first processing method:
The first step: it is more than 90% white lime powder that unslaked lime slaking is made to calcium hydroxide content;
Second step: water, urea, catalyzer, white lime powder are uniformly mixed and are mixed with uniform urea lime slurry, urea content is controlled at 5～38% preferably 15%～25%, calcium hydroxide content is pressed calcium oxide: urea mol ratio 0.2～1.2 is 1.0～1.05 preparations preferably, and catalyzer is by 0.5%～3% preferably 1.4%～1.7% preparation of weight of urea.
The 3rd step: chlorine bleach liquor's preparation: obtain chlorine bleach liquor to passing into chlorine in certain density caustic soda soln, control the available chlorine [Cl in chlorine bleach liquor
2] content is the preferred 100g/l～120g/l of 80g/l～140g/l, presses available chlorine [Cl simultaneously
2] 0.2～1.4 times of content preferred 1.0～1.1 times of free alkali contents of controlling in clorox.
The 4th step: by the chlorine bleach liquor of containing caustic soda and urea lime slurry by urea: clorox mol ratio is 0.9～1.1 preferably 0.98～1.05 to mix, be heated to 100 ℃～130 ℃ preferably 105 ℃～108 ℃ reactions, the causticizing reaction that has completed sodium carbonate and calcium hydroxide in reaction oxo-synthesis of hydrazine hydrate, the causticization that reaction obtains containing 4% left and right hydrazine hydrate completes liquid.
The 5th step: the causticization that contains lower concentration hydration hydrazine is completed to liquid through settling vessel sedimentation, the sedimentation mud of settling vessel bottom takes out and obtains calcium carbonate solid (can be processed into light calcium carbonate or cement) through Filter Press, settling vessel upper strata obtains mainly containing the causticization clear liquid of sodium-chlor, caustic soda, hydrazine hydrate and water, causticization clear liquid is again after the post-processing units such as evaporation, rectifying, solid-liquid separation, and obtaining respectively hydrazine content is 80% commodity hydrazine hydrate, the solid sodium chloride for electrolysis capable of circulation, the caustic soda soln for hydrazine hydrate building-up reactions capable of circulation.
Reaction equation:
NaClO+2NaOH+(NH
2)
2CO＝NaCl+Na
2CO
3+N
2H
4.H
2O
Na
2CO
3+Ca(OH)
2＝2NaOH+CaCO
3↓
(2) the second processing method:
The first step: it is more than 90% white lime powder that unslaked lime slaking is made to calcium hydroxide content;
Second step: urea, catalyzer are added in metering water and be mixed with uniform urea soln, and urea concentration is mixed with the preferred 300g/l～380g/l of 200g/l～420g/l, catalyzer is by 0.5%～3% preferably 1.4%～1.7% preparation of weight of urea;
The 3rd step: chlorine bleach liquor's preparation, in certain density caustic soda soln, pass into chlorine, control available chlorine [Cl in clorox
2] content is the preferred 100g/l～120g/l of 80g/l～140g/l, by available chlorine [Cl
2] 0.2～1.35 times of content preferred 1.0～1.1 times of free alkali contents of controlling in clorox.
The 4th step: by the chlorine bleach liquor of containing caustic soda and urea soln by urea: clorox mol ratio is 0.9～1.1 preferably 0.98～1.05 to mix, and is heated to 105 ℃～108 ℃ reactions, and reaction obtains the synthetic liquid that contains 4% left and right hydrazine hydrate,
The 5th step: will synthesize liquid and be chilled to 0～-5 ℃ and make crystallization Sodium carbonate decahydrate, filtering and obtaining carbonate content is 3～6% the freezing mother liquor of hydrazine hydrate, filters the Sodium carbonate decahydrate obtaining, and accounts for 40%～50% of sodium carbonate total amount after Sodium carbonate decahydrate is pure.
The 6th step: the freezing mother liquor of hydrazine hydrate, white lime powder, water are mixed in proportion and make uniform milk of lime hydrazine hydrate mother liquor, the concentration of controlling its sodium carbonate is 2%～6% preferably 4%～5%, press calcium oxide: sodium carbonate mol ratio 0～1.2 is 1.0～1.05 interpolation white lime powder preferably, after the causticizing reaction of certain hour (approximately 50～150 minutes), causticizing efficiency is reached more than 90% obtain causticization to complete liquid.
The 7th step: the causticization that contains lower concentration hydration hydrazine is completed to liquid through settling vessel sedimentation, the sedimentation mud of settling vessel bottom takes out and obtains calcium carbonate solid (can be processed into light calcium carbonate or cement) through Filter Press, settling vessel upper strata obtains mainly containing the causticization clear liquid of sodium-chlor, caustic soda, hydrazine hydrate and water, causticization clear liquid is again after the post-processing units such as evaporation, rectifying, solid-liquid separation, and obtaining respectively hydrazine content is 80% commodity hydrazine hydrate, the solid sodium chloride for electrolysis capable of circulation, the caustic soda soln for hydrazine hydrate building-up reactions capable of circulation.
Reaction equation:
NaClO+2NaOH+(NH
2)
2CO＝NaCl+Na
2CO
3+N
2H
4.H
2O
Na
2CO
3+Ca(OH)
2＝2NaOH+CaCO
3↓
(3) the third processing method:
The first step: it is more than 90% white lime powder that unslaked lime slaking is made to calcium hydroxide content;
Second step: urea, catalyzer are added in metering water and be mixed with uniform urea soln, and urea concentration is mixed with the preferred 300g/l～380g/l of 200g/l～420g/l, catalyzer is by 0.5%～3% preferably 1.4%～1.7% preparation of weight of urea;
The 3rd step: chlorine bleach liquor's preparation: obtain chlorine bleach liquor to passing into chlorine in certain density caustic soda soln, control the available chlorine [Cl in chlorine bleach liquor
2] content is the preferred l00g/l～120g/l of 80g/l～140g/l, presses available chlorine [Cl simultaneously
2] 0.2～1.4 times of content preferred 1.0～1.1 times of free alkali contents of controlling in clorox.
The 4th step: by chlorine bleach liquor and urea soln by urea: clorox mol ratio is 0.9～1.1 preferably 0.98～1.05 to mix, and is heated to 105 ℃～108 ℃ reactions, and reaction obtains the synthetic liquid that contains 4% left and right hydrazine hydrate,
The 5th step: will synthesize liquid, white lime powder, water and be mixed in proportion and make uniform lime slurry, the concentration of controlling sodium carbonate is 4%～11% preferably 6%～7%, press calcium oxide: sodium carbonate mol ratio 0～1.2 is 1.0～1.05 interpolation white lime powder preferably, after the causticizing reaction of 50～150 minutes, causticizing efficiency is reached more than 90% obtain causticization to complete liquid.
The 6th step: the causticization that contains lower concentration hydration hydrazine is completed to liquid through settling vessel sedimentation, the sedimentation mud of settling vessel bottom takes out and obtains calcium carbonate solid (can be processed into light calcium carbonate or cement) through Filter Press, settling vessel upper strata obtains mainly containing the causticization clear liquid of sodium-chlor, caustic soda, hydrazine hydrate and water, causticization clear liquid is again after the post-processing units such as evaporation, rectifying, solid-liquid separation, and obtaining respectively hydrazine content is 80% commodity hydrazine hydrate, the solid sodium chloride for electrolysis capable of circulation, the caustic soda soln for hydrazine hydrate building-up reactions capable of circulation.
Reaction equation:
NaClO+2NaOH+(NH
2)
2CO＝NaCl+Na
2CO
a+N
2H
4.H
2O
Na
2CO
3+Ca(OH)
2＝2NaOH+CaCO
3↓
A kind of hydrazine hydrate green circulatory new process of production as above, it is characterized in that: when the present invention has used calcium hydroxide by hydrazine hydrate building-up reactions, the first causticization of the sodium carbonate of by-product changes into calcium carbonate and sodium hydroxide, the causticization that obtains containing lower concentration hydration hydrazine completes liquid, causticization is completed to liquid to be clarified, solids removed by filtration calcium carbonate, obtain mainly containing sodium-chlor, caustic soda, the causticization clear liquid of hydrazine hydrate and water, causticization clear liquid evaporates again, rectifying, after the post-processing units such as solid-liquid separation, obtain respectively hydrazine content and be 80% commodity hydrazine hydrate, solid sodium chloride for electrolysis capable of circulation, caustic soda soln for hydrazine hydrate building-up reactions capable of circulation.
This technique greatly reduces the caustic soda consumption of hydrazine hydrate production, improved the recovery purity of by product sodium-chlor, thoroughly solved the waste liquor discharge pollution on the environment producing in current hydrazine hydrate synthesis technique, this technique has been accomplished low equipment investment, energy consumption is low, cost is low, simple to operate, level of automation is high, very practical as chlorine industry and the supporting deep processed product technique of caustic soda.
Four, embodiments of the invention:
Embodiment mono-:
The first step: starting material are prepared
Urea: N% >=46%
Caustic soda: NaOH% >=30%
Chlorine: Cl
2%>=95%
Catalyzer: magnesium chloride hexahydrate, content is greater than 95%.
White lime powder: calcium hydroxide content is 91%
Second step: water, urea, catalyzer, white lime powder are uniformly mixed and are mixed with uniform urea lime slurry, urea content is mixed with 15%, calcium hydroxide content is pressed calcium oxide: urea mol ratio 1.05 preparations, catalyzer is by 1.6% preparation of weight of urea.
The 3rd step: chlorine bleach liquor's preparation, at 25 ℃, chlorine is passed in certain density caustic soda soln, make available chlorine [Cl in clorox
2] content is mixed with 110g/l, the free alkali content in clorox is pressed available chlorine [Cl
2] 1.0 times of preparations of content.
The 4th step: by the chlorine bleach liquor of containing caustic soda and urea lime slurry by urea: clorox mol ratio is 0.9～1.2 to mix, be heated to 105 ℃～108 ℃ reactions 2～180 seconds, in reaction oxo-synthesis of hydrazine hydrate, completed the causticizing reaction of sodium carbonate and calcium hydroxide, the causticization that reaction obtains containing 4% left and right hydrazine hydrate completes liquid, detects causticizing efficiency and is respectively 93.6%～95.1%.
The 5th step: the causticization that contains lower concentration hydration hydrazine is completed to liquid through settling vessel sedimentation, the sedimentation mud of settling vessel bottom takes out and obtains calcium carbonate solid (can be processed into light calcium carbonate or cement) through Filter Press, settling vessel upper strata obtains mainly containing the causticization clear liquid of sodium-chlor, caustic soda, hydrazine hydrate and water, causticization clear liquid is again after the post-processing units such as evaporation, rectifying, solid-liquid separation, and obtaining respectively hydrazine content is 80% commodity hydrazine hydrate, the solid sodium chloride for electrolysis capable of circulation, the caustic soda soln for hydrazine hydrate building-up reactions capable of circulation.
Change urea: clorox mol ratio is carried out the experiment statistics table of hydrazine hydrate building-up reactions:
| Experiment numbers | 1# | 2# | 3# | 4# | 5# | 6# | 7# |
| Urea and time sodium mol ratio | 0.9 | 0.95 | 0.98 | 1.0 | 1.05 | 1.1 | 1.2 |
| With ureometer hydrazine hydrate yield % | 78.0 | 79.5 | 78.5 | 78.3 | 78.2 | 75.0 | 68.0 |
| The following sodium meter hydrazine hydrate yield % | 70.2 | 75.5 | 76.9 | 78.3 | 82.1 | 82.5 | 81.6 |
| Sodium carbonate causticization rate % | 93.6 | 93.3 | 94.3 | 95.1 | 94.6 | 94.3 | 94.0 |
Embodiment bis-:
The first step: starting material are prepared
Urea: N% >=46%
Caustic soda: NaOH% >=30%
Chlorine: Cl
2%>=95%
Catalyzer: magnesium chloride hexahydrate, content is greater than 95%.
White lime powder: calcium hydroxide content is 91%
Second step: water, urea, catalyzer, white lime powder are uniformly mixed and are mixed with uniform urea lime slurry, urea content is mixed with 5%～38%, calcium hydroxide content is pressed calcium oxide: urea mol ratio 1.05 preparations, catalyzer is by 1.6% preparation of weight of urea.
The 3rd step: chlorine bleach liquor's preparation, at 25 ℃, chlorine is passed in certain density caustic soda soln, make available chlorine [Cl in clorox
2] content is mixed with 110g/l, the free alkali content in clorox is pressed available chlorine [Cl
2] 1.0 times of preparations of content.
The 4th step: by 150ml chlorine bleach liquor and urea lime slurry by urea: clorox mol ratio is 1.0 to mix, be heated to 105 ℃～108 ℃ reactions 2～180 seconds, in reaction oxo-synthesis of hydrazine hydrate, completed the causticizing reaction of partial sodium carbonate and calcium hydroxide, the causticization that reaction obtains containing 4% left and right hydrazine hydrate completes liquid, detects causticizing efficiency and is respectively 83%～96.3%.
The 5th step: the causticization that contains lower concentration hydration hydrazine is completed to liquid through settling vessel sedimentation, the sedimentation mud of settling vessel bottom takes out and obtains calcium carbonate solid (can be processed into light calcium carbonate or cement) through Filter Press, settling vessel upper strata obtains mainly containing the causticization clear liquid of sodium-chlor, caustic soda, hydrazine hydrate and water, causticization clear liquid is again after the post-processing units such as evaporation, rectifying, solid-liquid separation, and obtaining respectively hydrazine content is 80% commodity hydrazine hydrate, the solid sodium chloride for electrolysis capable of circulation, the caustic soda soln for hydrazine hydrate building-up reactions capable of circulation.
In change urea lime slurry, the compound concentration of urea carries out the experiment statistics table of hydrazine hydrate building-up reactions:
| Experiment numbers | 1# | 2# | 3# | 4# | 5# | 6# | 7# |
| Urea concentration % | 5 | 8 | 10 | 12 | 15 | 19 | 23 |
| With ureometer hydrazine hydrate yield % | 76.5 | 77.0 | 78.5 | 78.3 | 78.2 | 77.8 | 78.0 |
| The following sodium meter hydrazine hydrate yield % | 76.5 | 77.0 | 78.5 | 78.3 | 78.2 | 77.8 | 78.0 |
| Sodium carbonate causticization rate % | 96.3 | 96.1 | 95.3 | 95.1 | 94.8 | 91.5 | 88.0 |
| Experiment numbers | 8# | 9# | 10# | 11# | 12# | 10# | ? |
| Urea concentration % | 25 | 28 | 32 | 36 | 38 | ? | ? |
| With ureometer hydrazine hydrate yield % | 77.3 | 75.5 | 74.3 | 73 | 71.5 | ? | ? |
| The following sodium meter hydrazine hydrate yield % | 77.3 | 75.5 | 74.3 | 73 | 71.5 | ? | ? |
| Sodium carbonate causticization rate % | 87 | 85 | 83 | 82 | 79 | ? | ? |
Embodiment tri-:
The first step: starting material are prepared
Urea: N% >=46%
Caustic soda: NaOH% >=30%
Chlorine: Cl
2%>=95%
Catalyzer: magnesium chloride hexahydrate, content is greater than 95%.
White lime powder: calcium hydroxide content is 91%
Second step: water, urea, catalyzer, white lime powder are uniformly mixed and are mixed with uniform urea lime slurry, urea content is mixed with 15%, calcium hydroxide content is pressed calcium oxide: urea mol ratio 1.05 preparations, catalyzer is by 1.6% preparation of weight of urea.
The 3rd step: chlorine bleach liquor's preparation, at 25 ℃, chlorine is passed in certain density caustic soda soln, control available chlorine [Cl in clorox
2] content is 110g/l, by available chlorine [Cl
2] 0.2～1.35 times of the content free alkali content of controlling in clorox.
The 4th step: by 150ml chlorine bleach liquor and urea lime slurry by urea: clorox mol ratio is 1.0 to mix, be heated to 105 ℃～108 ℃ reactions 2～180 seconds, in reaction oxo-synthesis of hydrazine hydrate, completed the causticizing reaction of sodium carbonate and calcium hydroxide, the causticization that reaction obtains containing 4% left and right hydrazine hydrate completes liquid, detects causticizing efficiency and is respectively 60.1%～95.2%.
The 5th step: the causticization that contains lower concentration hydration hydrazine is completed to liquid through settling vessel sedimentation, the sedimentation mud of settling vessel bottom takes out and obtains calcium carbonate solid (can be processed into light calcium carbonate or cement) through Filter Press, settling vessel upper strata obtains mainly containing the causticization clear liquid of sodium-chlor, caustic soda, hydrazine hydrate and water, causticization clear liquid is again after the post-processing units such as evaporation, rectifying, solid-liquid separation, and obtaining respectively hydrazine content is 80% commodity hydrazine hydrate, the solid sodium chloride for electrolysis capable of circulation, the caustic soda soln for hydrazine hydrate building-up reactions capable of circulation.
In change chlorine bleach liquor, the proportioning of free alkali is carried out the experiment statistics table of hydrazine hydrate building-up reactions:
| Experiment numbers | 1# | 2# | 3# | 4# | 5# | 6# | 7# |
| Inferior sodium free alkali: [Cl 2] proportioning | 0.2 | 0.5 | 0.8 | 0.9 | 1.0 | 1.15 | 1.25 |
| With ureometer hydrazine hydrate yield % | 15.6 | 45.6 | 75.3 | 77.5 | 78.5 | 78.8 | 78.6 |
| The following sodium meter hydrazine hydrate yield % | 15.6 | 45.6 | 75.3 | 77.5 | 78.5 | 78.8 | 78.6 |
| Sodium carbonate causticization rate % | 93.5 | 93.1 | 94.5 | 95.2 | 95.3 | 90.7 | 83.0 |
| Experiment numbers | 8# | 9# | ? | ? | ? | ? | ? |
| Inferior sodium free alkali: [Cl2] proportioning | 1.3 | 1.35 | ? | ? | ? | ? | ? |
| With ureometer hydrazine hydrate yield % | 78.7 | 78.6 | ? | ? | ? | ? | ? |
| The following sodium meter hydrazine hydrate yield % | 78.7 | 78.6 | ? | ? | ? | ? | ? |
| Sodium carbonate causticization rate % | 76 | 60.1 | ? | ? | ? | ? | ? |
Embodiment tetra-:
The first step: starting material are prepared
Urea: N% >=46%
Caustic soda: NaOH% >=30%
Chlorine: Cl
2%>=95%
Catalyzer: magnesium chloride hexahydrate, content is greater than 95%.
White lime powder: calcium hydroxide content is 91%
Second step: water, urea, catalyzer, white lime powder are uniformly mixed and are mixed with uniform urea lime slurry, urea content is mixed with 15%, calcium hydroxide content is pressed calcium oxide: urea mol ratio 1.05 preparations, catalyzer is by 1.6% preparation of weight of urea.
The 3rd step: chlorine bleach liquor's preparation, at 25 ℃, chlorine is passed in certain density caustic soda soln, make available chlorine [Cl in clorox
2] content is mixed with 80g/l～140g/l, the free alkali content in clorox is pressed available chlorine [Cl
2] 1.0 times of preparations of content.
The 4th step: by 150ml chlorine bleach liquor and urea lime slurry by urea: clorox mol ratio is 1.0 to mix, be heated to 105 ℃～108 ℃ reactions 2～180 seconds, in reaction oxo-synthesis of hydrazine hydrate, completed the causticizing reaction of sodium carbonate and calcium hydroxide, the causticization that reaction obtains containing 4% left and right hydrazine hydrate completes liquid, detects causticizing efficiency and is respectively 67.1%～97.5%.
The 5th step: the causticization that contains lower concentration hydration hydrazine is completed to liquid through settling vessel sedimentation, the sedimentation mud of settling vessel bottom takes out and obtains calcium carbonate solid (can be processed into light calcium carbonate or cement) through Filter Press, settling vessel upper strata obtains mainly containing the causticization clear liquid of sodium-chlor, caustic soda, hydrazine hydrate and water, causticization clear liquid is again after the post-processing units such as evaporation, rectifying, solid-liquid separation, and obtaining respectively hydrazine content is 80% commodity hydrazine hydrate, the solid sodium chloride for electrolysis capable of circulation, the caustic soda soln for hydrazine hydrate building-up reactions capable of circulation.
Available chlorine [Cl in change chlorine bleach liquor
2] concentration carry out the experiment statistics table of hydrazine hydrate building-up reactions:
| Experiment numbers | 1# | 2# | 3# | 4# | 5# | 6# | 7# |
[0091]?
| Inferior sodium [Cl 2] concentration g/l | 80 | 90 | 100 | 105 | 110 | 115 | 120 |
| With ureometer hydrazine hydrate yield % | 78.9 | 78.5 | 78.5 | 78.9 | 78.5 | 78.8 | 77.9 |
| The following sodium meter hydrazine hydrate yield % | 78.9 | 78.5 | 78.5 | 78.9 | 78.5 | 78.8 | 77.9 |
| Sodium carbonate causticization rate % | 97.5 | 97.1 | 95.3 | 95.1 | 95.3 | 90.7 | 86.0 |
| Experiment numbers | 8# | 9# | ? | ? | ? | ? | ? |
| Inferior sodium [Cl2] concentration g/l | 130 | 140 | ? | ? | ? | ? | ? |
| With ureometer hydrazine hydrate yield % | 75.5 | 73.2 | ? | ? | ? | ? | ? |
| The following sodium meter hydrazine hydrate yield % | 75.5 | 73.2 | ? | ? | ? | ? | ? |
| Sodium carbonate causticization rate % | 80.6 | 67.1 | ? | ? | ? | ? | ? |
Embodiment five:
The first step: starting material are prepared
Urea: N% >=46%
Caustic soda: NaOH% >=30%
Chlorine: Cl
2%>=95%
Catalyzer: magnesium chloride hexahydrate, content is greater than 95%.
White lime powder: calcium hydroxide content is 91%
Second step: water, urea, catalyzer, white lime powder are uniformly mixed and are mixed with uniform urea lime slurry, urea content is mixed with 15%, calcium hydroxide content is pressed calcium oxide: urea mol ratio 0.0～1.15 preparation, catalyzer is by 1.6% preparation of weight of urea.
The 3rd step: chlorine bleach liquor's preparation, at 25 ℃, chlorine is passed in certain density caustic soda soln, make available chlorine [Cl in clorox
2] content is mixed with 110g/l, the free alkali content in clorox is pressed available chlorine [Cl
2] 1.0 times of preparations of content.
The 4th step: by 150ml chlorine bleach liquor and urea lime slurry by urea: clorox mol ratio is 1.0 to mix, be heated to 105 ℃～108 ℃ reactions 2～180 seconds, in reaction oxo-synthesis of hydrazine hydrate, completed the causticizing reaction of partial sodium carbonate and calcium hydroxide, the causticization that reaction obtains containing 4% left and right hydrazine hydrate completes liquid, detects causticizing efficiency and is respectively 65%～96%.
The 5th step: the causticization that contains lower concentration hydration hydrazine is completed to liquid through settling vessel sedimentation, the sedimentation mud of settling vessel bottom takes out and obtains calcium carbonate solid (can be processed into light calcium carbonate or cement) through Filter Press, settling vessel upper strata obtains mainly containing the causticization clear liquid of sodium-chlor, caustic soda, hydrazine hydrate and water, causticization clear liquid is again after the post-processing units such as evaporation, rectifying, solid-liquid separation, and obtaining respectively hydrazine content is 80% commodity hydrazine hydrate, the solid sodium chloride for electrolysis capable of circulation, the caustic soda soln for hydrazine hydrate building-up reactions capable of circulation.
Change calcium oxide: urea mole proportioning is carried out the experiment statistics table of hydrazine hydrate building-up reactions:
| Experiment numbers | 1# | 2# | 3# | 4# | 5# | 6# | 7# |
| Calcium oxide: urea mole proportioning | 0.0 | 0.5 | 0.8 | 0.9 | 1.0 | 1.05 | 1.15 |
[0105]?
| With ureometer hydrazine hydrate yield % | 78.2 | 79.3 | 78.3 | 78.9 | 78.8 | 78.7 | 78.9 |
| The following sodium meter hydrazine hydrate yield % | 78.2 | 79.3 | 78.3 | 78.9 | 78.8 | 78.7 | 78.9 |
| Sodium carbonate causticization rate % | 0.0 | 49.1 | 78.0 | 87.6 | 94.1 | 95.7 | 95.4 |
Embodiment six:
The first step: starting material are prepared
Urea: N% >=46%
Caustic soda: NaOH% >=30%
Chlorine: Cl
2%>=95%
Catalyzer: magnesium chloride hexahydrate, content is greater than 95%.
White lime powder: calcium hydroxide content is 91%
Second step: water, urea, catalyzer are uniformly mixed and are mixed with uniform urea soln, and urea content is mixed with 300g/l, catalyzer is by 1.6% preparation of weight of urea.
The 3rd step: chlorine bleach liquor's preparation, at 25 ℃, chlorine is passed in certain density caustic soda soln, make available chlorine [Cl in clorox
2] content is mixed with 110g/l, the free alkali content in clorox is pressed available chlorine [Cl
2] 1.15 times of preparations of content.
The 4th step: by 150ml chlorine bleach liquor and urea soln liquid by urea: clorox mol ratio is 1.0 to mix, be heated to 105 ℃～108 ℃ reactions 2～180 seconds, obtain the synthetic liquid 232g containing hydrazine hydrate 3.89%, by synthetic liquid first the freezing crystallize sodium carbonate wherein that makes become Sodium carbonate decahydrate, remove by filter the freezing mother liquor 200g of hydrazine hydrate that to obtain containing sodium carbonate after Sodium carbonate decahydrate be 5.4%.
The 5th step: in freezing mother liquor by calcium oxide: sodium carbonate mol ratio is 0～1.2 to add white lime powder, add certain water to make concentration of sodium carbonate be controlled at 4%, stir evenly and send into causticizing tank insulation carry out causticization between 95 ℃～98 ℃, causticization after 50～150 minutes causticizing efficiency reach and more than 90% be causticization and complete liquid.
The 6th step: the causticization that contains lower concentration hydration hydrazine is completed to liquid through settling vessel sedimentation, the sedimentation mud of settling vessel bottom takes out and obtains calcium carbonate solid (can be processed into light calcium carbonate or cement) through Filter Press, settling vessel upper strata obtains mainly containing the causticization clear liquid of sodium-chlor, caustic soda, hydrazine hydrate and water, causticization clear liquid is again after the post-processing units such as evaporation, rectifying, solid-liquid separation, and obtaining respectively hydrazine content is 80% commodity hydrazine hydrate, the solid sodium chloride for electrolysis capable of circulation, the caustic soda soln for hydrazine hydrate building-up reactions capable of circulation.
Change calcium oxide: sodium carbonate mol ratio is carried out the experiment statistics table of causticizing reaction to the freezing mother liquor of hydrazine hydrate:
| Experiment numbers | 1# | 2# | 3# | 4# | 5# | 6# | 7# |
| Calcium oxide: sodium carbonate mol ratio | 0.0 | 0.5 | 0.8 | 0.9 | 1.0 | 1.05 | 1.1 |
| Sodium carbonate causticization rate % | 0.0 | 45.7 | 72.3 | 81.2 | 89.1 | 90.6 | 90.5 |
| Experiment numbers | 8# | 9# | ? | ? | ? | ? | ? |
| Calcium oxide: sodium carbonate mol ratio | 1.15 | 1.2 | ? | ? | ? | ? | ? |
| Sodium carbonate causticization rate % | 91.0 | 91.1 | ? | ? | ? | ? | ? |
[0120]embodiment seven:
The first step: starting material are prepared
Urea: N% >=46%
Caustic soda: NaOH% >=30%
Chlorine: Cl
2%>=95%
Catalyzer: magnesium chloride hexahydrate, content is greater than 95%.
White lime powder: calcium hydroxide content is 91%
Second step: water, urea, catalyzer are uniformly mixed and are mixed with uniform urea soln, and urea content is mixed with 300g/l, catalyzer is by 1.6% preparation of weight of urea.
The 3rd step: chlorine bleach liquor's preparation, at 25 ℃, chlorine is passed in certain density caustic soda soln, make available chlorine [Cl in clorox
2] content is mixed with 110g/l, the free alkali content in clorox is pressed available chlorine [Cl
2] 1.15 times of preparations of content.
The 4th step: by 150ml chlorine bleach liquor and urea soln liquid by urea: clorox mol ratio is 1.0 to mix, be heated to 105 ℃～108 ℃ reactions 2～180 seconds, obtain the synthetic liquid 232g containing hydrazine hydrate 3.89%, by synthetic liquid first the freezing crystallize sodium carbonate wherein that makes become Sodium carbonate decahydrate, remove by filter the freezing mother liquor 200g of hydrazine hydrate that to obtain containing sodium carbonate after Sodium carbonate decahydrate be 6%.
The 5th step: in freezing mother liquor by calcium oxide: sodium carbonate mol ratio is 1.05 to add white lime powder, adding water dilutes and makes concentration of sodium carbonate be controlled at respectively 2%～6%, stir evenly and send into causticizing tank insulation carry out causticization between 95 ℃～98 ℃, causticization after 50～150 minutes causticizing efficiency reach and more than 90% be causticization and complete liquid.
The 6th step: the causticization that contains lower concentration hydration hydrazine is completed to liquid through settling vessel sedimentation, the sedimentation mud of settling vessel bottom takes out and obtains calcium carbonate solid (can be processed into light calcium carbonate or cement) through Filter Press, settling vessel upper strata obtains mainly containing the causticization clear liquid of sodium-chlor, caustic soda, hydrazine hydrate and water, causticization clear liquid is again after the post-processing units such as evaporation, rectifying, solid-liquid separation, and obtaining respectively hydrazine content is 80% commodity hydrazine hydrate, the solid sodium chloride for electrolysis capable of circulation, the caustic soda soln for hydrazine hydrate building-up reactions capable of circulation.
Change thin up ratio is carried out the experiment statistics table of causticizing reaction to the freezing mother liquor of hydrazine hydrate:
| Experiment numbers | 1# | 2# | 3# | 4# | 5# | 6# | 7# |
| Carbonate content % after dilution | 2 | 3 | 4 | 4.5 | 5 | 5.5 | 6.0 |
| Sodium carbonate causticization rate % | 91.9 | 91.7 | 91.5 | 91.2 | 90.5 | 88.2 | 86.5 |
Embodiment eight:
The first step: starting material are prepared
Urea: N% >=46%
Caustic soda: NaOH% >=30%
Chlorine: Cl
2%>=95%
Catalyzer: magnesium chloride hexahydrate, content is greater than 95%.
White lime powder: calcium hydroxide content is 91%
Second step: water, urea, catalyzer are uniformly mixed and are mixed with uniform urea soln, and urea content is mixed with 300g/l, catalyzer is by 1.6% preparation of weight of urea.
The 3rd step: chlorine bleach liquor's preparation, at 25 ℃, chlorine is passed in certain density caustic soda soln, make available chlorine [Cl in clorox
2] content is mixed with 110g/l, the free alkali content in clorox is pressed available chlorine [Cl
2] 1.15 times of preparations of content.
The 4th step: by 150ml chlorine bleach liquor and urea soln liquid by urea: clorox mol ratio is 1.0 to mix, and is heated to 105 ℃～108 ℃ reactions 120～180 seconds, obtains the synthetic liquid 232g containing hydrazine hydrate 3.89%.
The 5th step: in the synthetic liquid of hydrazine hydrate by calcium oxide: sodium carbonate mol ratio is 0～1.2 to add white lime powder, adding water dilutes and makes carbonate content be controlled at 6%, stir evenly and send into causticizing tank insulation and between 95 ℃～98 ℃, carry out the causticization of 50～150 minutes, causticizing efficiency is reached more than 90% be causticization to complete liquid.
The 6th step: the causticization that contains lower concentration hydration hydrazine is completed to liquid through settling vessel sedimentation, the sedimentation mud of settling vessel bottom takes out and obtains calcium carbonate solid (can be processed into light calcium carbonate or cement) through Filter Press, settling vessel upper strata obtains mainly containing the causticization clear liquid of sodium-chlor, caustic soda, hydrazine hydrate and water, causticization clear liquid is again after the post-processing units such as evaporation, rectifying, solid-liquid separation, and obtaining respectively hydrazine content is 80% commodity hydrazine hydrate, the solid sodium chloride for electrolysis capable of circulation, the caustic soda soln for hydrazine hydrate building-up reactions capable of circulation.
Change calcium oxide: sodium carbonate mol ratio is carried out the experiment statistics table of causticizing reaction to the synthetic liquid of hydrazine hydrate:
| Experiment numbers | 1# | 2# | 3# | 4# | 5# | 6# | 7# |
| Calcium oxide: sodium carbonate mol ratio | 0.0 | 0.5 | 0.8 | 0.9 | 1.0 | 1.05 | 1.1 |
| Sodium carbonate causticization rate % | 0 | 45.8 | 72.6 | 81.2 | 89.3 | 91.7 | 91.5 |
| Experiment numbers | 8# | 9# | ? | ? | ? | ? | ? |
| Calcium oxide: sodium carbonate mol ratio | 1.15 | 1.2 | ? | ? | ? | ? | ? |
| Sodium carbonate causticization rate % | 91.5 | 91.8 | ? | ? | ? | ? | ? |
Embodiment nine:
The first step: starting material are prepared
Urea: N% >=46%
Caustic soda: NaOH% >=30%
Chlorine: Cl
2%>=95%
Catalyzer: magnesium chloride hexahydrate, content is greater than 95%.
White lime powder: calcium hydroxide content is 91%
Second step: water, urea, catalyzer are uniformly mixed and are mixed with uniform urea soln, and urea content is mixed with 380g/l, catalyzer is by 1.6% preparation of weight of urea.
The 3rd step: chlorine bleach liquor's preparation, at 25 ℃, chlorine is passed in certain density caustic soda soln, make available chlorine [Cl in clorox
2] content is mixed with 115g/l, the free alkali content in clorox is pressed available chlorine [Cl
2] 1.2 times of preparations of content.
The 4th step: by 150ml chlorine bleach liquor and urea soln liquid by urea: clorox mol ratio is 1.0 to mix, and is heated to 105 ℃～108 ℃ reactions 2～180 seconds, obtains the synthetic liquid 212g containing 5.0% hydrazine hydrate, 11% sodium carbonate.
The 5th step: in the synthetic liquid of hydrazine hydrate by calcium oxide: sodium carbonate mol ratio is 1.05 to add white lime powder, adding water dilutes and makes carbonate content be controlled at respectively 4%～11%, stir evenly and send into causticizing tank insulation and between 95 ℃～98 ℃, carry out the causticization of 50～150 minutes, causticizing efficiency is reached more than 90% be causticization to complete liquid.
The 6th step: the causticization that contains lower concentration hydration hydrazine is completed to liquid through settling vessel sedimentation, the sedimentation mud of settling vessel bottom takes out and obtains calcium carbonate solid (can be processed into light calcium carbonate or cement) through Filter Press, settling vessel upper strata obtains mainly containing the causticization clear liquid of sodium-chlor, caustic soda, hydrazine hydrate and water, causticization clear liquid is again after the post-processing units such as evaporation, rectifying, solid-liquid separation, and obtaining respectively hydrazine content is 80% commodity hydrazine hydrate, the solid sodium chloride for electrolysis capable of circulation, the caustic soda soln for hydrazine hydrate building-up reactions capable of circulation.
Change thin up ratio is carried out the experiment statistics table of causticizing reaction to the synthetic liquid of hydrazine hydrate:
| Experiment numbers | 1# | 2# | 3# | 4# | 5# | 6# | 7# |
| Carbonate content % after dilution | 4 | 5 | 6 | 6.5 | 7 | 8 | 11 |
| Sodium carbonate causticization rate % | 91.5 | 91.3 | 90.5 | 90.2 | 90.1 | 87 | 82.1 |
Claims (1)
1. a hydrazine hydrate green circulatory new process of production, it is characterized in that: when the present invention has used calcium hydroxide by hydrazine hydrate building-up reactions, the first causticization of the sodium carbonate of by-product changes into calcium carbonate and sodium hydroxide, the causticization that obtains containing lower concentration hydration hydrazine completes liquid, causticization is completed to liquid to be clarified, solids removed by filtration calcium carbonate, obtain mainly containing sodium-chlor, caustic soda, the causticization clear liquid of hydrazine hydrate and water, causticization clear liquid is again through evaporation, rectifying, after the post-processing units such as solid-liquid separation, obtain respectively hydrazine content and be 80% commodity hydrazine hydrate, solid sodium chloride for electrolysis capable of circulation, caustic soda soln for hydrazine hydrate building-up reactions capable of circulation.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104528658A (en) * | 2015-01-21 | 2015-04-22 | 江西省博浩源化工有限公司 | Method for preparing sodium percarbonate from hydrazine hydrate byproducts and product of method |
| CN105036098A (en) * | 2015-09-01 | 2015-11-11 | 青海盐湖工业股份有限公司 | Method for removing sodium carbonate in solution |
| CN112093783A (en) * | 2020-09-30 | 2020-12-18 | 重庆腾泽化学有限公司 | Hydrazine hydrate purification process |
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| CN101786643A (en) * | 2010-03-18 | 2010-07-28 | 福建省邵武市榕丰化工有限公司 | Method for comprehensively utilizing byproduct salt and alkali waste in production of hydrazine hydrate by urea process |
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