CN100389892C - Recovering treatment of hydrated hydrazine by-product saline-alkali by urea method - Google Patents
Recovering treatment of hydrated hydrazine by-product saline-alkali by urea method Download PDFInfo
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- CN100389892C CN100389892C CNB2005100218591A CN200510021859A CN100389892C CN 100389892 C CN100389892 C CN 100389892C CN B2005100218591 A CNB2005100218591 A CN B2005100218591A CN 200510021859 A CN200510021859 A CN 200510021859A CN 100389892 C CN100389892 C CN 100389892C
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- alkali
- slurry
- hydrazine hydrate
- sodium carbonate
- caustic soda
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- 239000003513 alkali Substances 0.000 title claims abstract description 55
- 238000000034 method Methods 0.000 title claims abstract description 36
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000004202 carbamide Substances 0.000 title claims abstract description 19
- 239000006227 byproduct Substances 0.000 title claims abstract description 18
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 title claims description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 129
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 84
- 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 claims abstract description 59
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 229910001868 water Inorganic materials 0.000 claims abstract description 44
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 42
- 150000003839 salts Chemical class 0.000 claims abstract description 38
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000012267 brine Substances 0.000 claims abstract description 13
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 12
- 239000012535 impurity Substances 0.000 claims abstract description 9
- 238000011084 recovery Methods 0.000 claims abstract description 7
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 87
- 235000002639 sodium chloride Nutrition 0.000 claims description 87
- 239000002002 slurry Substances 0.000 claims description 79
- 239000011780 sodium chloride Substances 0.000 claims description 53
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 42
- 239000012452 mother liquor Substances 0.000 claims description 30
- 239000000243 solution Substances 0.000 claims description 16
- 239000000203 mixture Substances 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000460 chlorine Substances 0.000 claims description 9
- 238000000926 separation method Methods 0.000 claims description 8
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 7
- 238000001354 calcination Methods 0.000 claims description 7
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- 239000002994 raw material Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 4
- 238000005352 clarification Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 230000005484 gravity Effects 0.000 claims description 4
- 238000010298 pulverizing process Methods 0.000 claims description 4
- 239000010865 sewage Substances 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 238000005065 mining Methods 0.000 claims description 2
- 238000001704 evaporation Methods 0.000 abstract description 9
- 230000008020 evaporation Effects 0.000 abstract description 9
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000004537 pulping Methods 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 3
- 239000005708 Sodium hypochlorite Substances 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000004134 energy conservation Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 abstract 1
- 238000007254 oxidation reaction Methods 0.000 abstract 1
- 235000017550 sodium carbonate Nutrition 0.000 description 33
- 239000000126 substance Substances 0.000 description 9
- 239000007789 gas Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000004458 analytical method Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 239000004604 Blowing Agent Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000001944 continuous distillation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000011027 product recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Abstract
The present invention discloses a method for recovering and treating byproducts in an evaporation process by producing hydrazine hydrate by the method of urea, sodium hypochlorite and sodium hydroxide oxidation. The present invention comprises a pulping step, a salt pulp and alkali pulp separating step, a treating step for salt pulp, a treating step for alkali pulp, and a mother liquid recycle pulping step. Because salt and alkali are separated in stages by being pulped with hot water, the present invention has the advantages of waste hot water discharge, high safety factor, energy conservation, easy operation, easy recovery of hydrazine hydrate, obviously advanced technology, etc. Monohydrated sodium carbonate with lower quality is treated by an incineration method, and calcined tail gas is absorbed by water so as to reduce the water content of sodium carbonate and the content of other impurities, improve the quality of recovered matter, increase the commodity value of the sodium carbonate, and simultaneously avoid the environment pollution caused by the calcined tail gas. The recovered solid salt is directly atomized into brine, and fine brine after treatment returns to an electric groove so as to truly realize the closed cycle production of a chlorine-alkali system.
Description
Technical field
The present invention relates to a kind of processing method of producing the accessory substance in the hydrazine hydrate process with urea, clorox, NaOH oxidizing process, more particularly, is the saline and alkaline method that recycles to institute's by-product in the evaporation process.
Background technology
Hydrazine hydrate has another name called: hydrazine hydrate, chemical formula: N
2H
4H
2O, molecular weight: 50.07, belong to fine chemical product.Hydrazine hydrate is as a kind of chemical intermediate, and its potential use and application are very extensive, mainly is divided into three aspects: one, produce plastics blowing agent; Its two, in the vapor recycle of power industry, it is used as and prevents that pipeline from getting rusty and aging in advance, thereby improves the security reliability in power station greatly; In addition, hydrazine hydrate also is important medicine and pesticide material.The various production methods of hydrazine hydrate, as draw west (Rashig) method, Bel's (Bayer) method or hydrogen peroxide method, the present invention is according to adopting urea, clorox, NaOH oxidizing process (abbreviation urea method), technological process is mainly as follows: with caustic soda, water, chlorine is raw material preparation liquor natrii hypochloritis, close the thick solution of hydrazine with the urea liquid water generation reaction, wherein contain sodium carbonate, sodium chloride, NaOH and water, the thick solution of hydrazine hydrate is through crystallisation by cooling, reclaim washing soda wherein, again solution is evaporated, water that evaporates and hydrazine hydrate steam carry out the hydrazine hydrate that rectifying obtains high-load again, the sodium carbonate of by-product in the evaporation process, sodium chloride and a small amount of hydrazine hydrate that is entrained with, saline and alkaline mixture such as NaOH and water.
The main chemical reactions equation of urea legal system hydrazine hydrate is:
Cl
2+2NaOH---NaClO+NaCl+H
2O
NaClO+N
2H
4CO+2NaOH---N
2H
4·H
2O+Na
2CO
3+NaCl
Its key reaction has two, and water generation reaction closes the thick solution of hydrazine, simultaneously by-product a large amount of sodium carbonate, sodium chloride, the chemical analysis of the saline and alkaline mixture that obtains after the hydrazine hydrate in the thick solution of hydrazine hydrate, the water evaporation is as follows:
Sodium chloride: 20-60% sodium carbonate: 10-35% caustic soda: 2-15%
N
2H
4H
2All the other 10-25% of O:0.2-1.0% are water and other trace impurity
As seen, there is following shortcoming in urea method production hydrazine hydrate method: the sodium chloride that stays in evaporation process, sodium carbonate, caustic soda, N
2H
4H
2O all has certain economic value, be unrealized in the past and reclaim entirely, such as Chinese patent 00120610.9 disclosed " a kind of method of separating the hydrazine hydrate alkali mud " and 01133711.7 disclosed " a kind of method of recycle-water hydrazine hydrate continuous distillation salt mud " and 02113204.6 disclosed " a kind of carbonization; the method for dried recovered hydrazine hydrate alkali mud ", these the three kinds methods of handling salt slurry all are that sodium chloride in the salt slurry and sodium carbonate are separated utilization, or caustic soda is converted into sodium carbonate recycles, but still exist the by-product recovery rate low, reclaim incomplete shortcoming, be difficult to realize that large-scale industry recycles, do not have the N that reclaims wherein as these methods
2H
4H
2O, directly enter in the rivers behind the dilute with water, caused the very big waste of resource, simultaneously, saline and alkaline mixture contains a certain amount of hydrazine hydrate and ammonia, if directly discharging,, be very serious to the pollution of environment because its ammonia nitrogen index exceeding standard reaches about 300--500 times (industrial wastewater qualified discharge ammonia nitrogen index is 15mg/l) and have higher basicity (pH value 〉=11).Therefore, how to realize that it is the technical problem that needs to be resolved hurrily in the current hydrazine hydrate production process to the pollution of environment that resource reclaims and make full use of, solves by-product saline-alkali entirely.
Summary of the invention
The present invention at first purpose is the separating and recovering processing method that provides a kind of urea method to produce the by-product saline-alkali that produces in the hydrazine hydrate process for addressing the above problem, can realize whole recyclings of accessory substance after using this method to the by-product saline-alkali separating treatment, the material that is discharged meets national requirements for environmental protection.
The object of the present invention is achieved like this:
(a) slurrying step: by-product saline-alkali in the urea method hydrazine hydrate reaction under stirring condition, is added temperature in 65-90 ℃ hot water, make solid-to-liquid ratio and be 0.3～0.8: 1 the slurries that contain sodium carbonate, sodium chloride, caustic soda, hydrazine hydrate.
(b) separating step of salt slurry and alkali slurry: (a) salt slurry that mainly contains sodium chloride and the alkali slurry that mainly contains sodium carbonate are arranged in the slurries that make in the step, utilize the gravity different mining of salt slurry and alkali slurry with classifying equipoment the salt slurry to be separated with the alkali slurry, obtaining solid-to-liquid ratio respectively is 0.6-1: 1 salt slurry and 0.3-0.6: 1 alkali slurry;
(c) treatment step of salt slurry: will be in (b) step isolated salt slurry after the centrifuge separation, obtain caustic soda content be 2～8% and sodium chloride content be 65～85% solid sodium chloride and mother liquor, the solid sodium chloride that obtains is configured to solution, adds between acid adjustment its pH value to 8～9 through adding water, being mixed with sodium chloride content is the refined brine of 200～300g/l, total ammonium content≤80ppm, send the chlor-alkali system as the raw material of producing chlorine and caustic soda this refined brine.
(d) treatment step of alkali slurry: will be in (b) step isolated alkali slurry to obtain carbonate content after the centrifuge separation be 45～65% monohydrated sodium carbonate and mother liquor, this monohydrated sodium carbonate sent in the rotary kiln under 150～500 ℃ of conditions calcine, calcination time was controlled at 1～5 hour, remove the moisture in the monohydrated sodium carbonate, obtain sodium carbonate through pulverizing behind caustic soda and other impurity, to calcine the tail gas that produces simultaneously absorbs with water circulation in the air exhauster suction absorption tower, tail gas absorbs the back emptying, and the absorption liquid that produces in the absorption tower send the sewage disposal collecting pit through behind the clarification filtration.
(e) mother liquor reuse slurrying step: two kinds of mother liquors that produce in the treatment step with the treatment step of salt slurry and alkali slurry separate the back remittance together by centrifuge, keeping delivering to the slurrying step under 60～90 ℃ of conditions, continuation as next time saline and alkaline mixture the slurrying medium and recycle, under stirring condition, in mother liquor, add by-product saline-alkali, when the solid-to-liquid ratio of slurries 0.3～0.8: 1, temperature configures slurries when being 80～95 ℃, no longer again, use hot water slurrying this moment, through behind the circulating pulp-making repeatedly, hydrazine hydrate in saline and alkaline and caustic soda constantly dissolve in the mother liquor, hydrazine hydrate rises to 5～15g/l in mother liquor, when caustic soda rises to 60～120g/l, with pump this mother liquor is returned vapo(u)rization system recovery hydrazine hydrate wherein, and the caustic soda that constantly consumes in the additional vapo(u)rization system.
The present invention has following advantage than prior art:
The present invention is because (1) adopts saline and alkaline with classification separation after the hot water slurrying, there is not successful precedent in the urea legal system hydrazine hydrate by-product saline-alkali recovery method both at home and abroad, this method is compared with adopting concentrated base or other medium slurrying, have solve spent hot water's discharging, safety coefficient height, energy savings, easy and simple to handle, reclaim advantage such as hydrazine hydrate easily, technical advance is obvious.And adopt concentrated base slurrying, have unsurmountable alkali consumption height, the big and centrifugal difficulty of hidden danger, slurry viscosity that concentrated base is hurted sb.'s feelings, too high basicity affects recovery shortcomings such as hydrazine hydrate wherein; (2) adopt method for calcinating to handle the lower monohydrated sodium carbonate of quality, and calcining tail gas is carried out water absorb, reduced moisture and other impurity content of sodium carbonate, improved the quality of regenerant, increased the commodity value of sodium carbonate, solved of the pollution of calcining tail gas simultaneously environment; (3) will reclaim solid salt and directly change into salt solution, and by washing, adding acid, obtain refined brine and return electric groove, and really realize chlor-alkali system lock circulation production, urea method is produced hydrazine hydrate technology and has been obtained qualitative leap.
Description of drawings
Fig. 1 is a technological process block-diagram of the present invention.
The specific embodiment
Below in conjunction with drawings and Examples the present invention is described in further detail, but the present invention has more than and is limited to these examples.
Step at first routinely prepares hydrazine hydrate, at first 30% caustic soda is put into the diluted alkaline make-up tank, is adding certain amount of industrial water, with pump constantly circulation to mix content be stand-by behind the 250-320g/l; Again industry water is put into urea liquid make-up tank, under agitation added solid urea and catalyst, treat that it is solution for later use behind the 250-320g/l that solid urea dissolves content; Then diluted alkaline is sent in the sodium hypochlorite reaction device by certain flow, fed chlorine, usefulness-5-5 ℃ of chilled brine cooling controlled reaction temperature and contained the liquor natrii hypochloritis that effective chlorine is 5-15% making below 30 ℃.Chemical equation:
2NaOH+Cl
2＝NaClO+NaCl+H
2O
With pump clorox and urea liquid are mixed the back by a certain percentage then and contain the thick solution of hydrazine hydrate, chemical equation to 100-110 ℃ of reaction generation with steam heated:
NaClO+N
2H4
CO+2NaOH＝N
2H
4·H
2O+Na
2CO
3+NaCl
The thick solution of hydrazine hydrate is cooled to＜sends in the crystallization kettle after 50 ℃ with pump then, with＜-5 ℃ liquefied ammonia or chilled brine cooling, after temperature was reduced to-2 ℃, centrifugation went out in the thick hydrazine hydrate solution 70% sodium carbonate.Send in the forced-circulation evaporator and evaporate removing the thick solution of hydrazine hydrate behind the sodium carbonate, water that evaporates and hydrazine hydrate steam enter again constantly carry in the rectifying column dense to 80%.The chemical analysis of the saline and alkaline mixture that obtains after the evaporation of the hydrazine hydrate in the thick solution of hydrazine hydrate, water is as follows:
Sodium chloride: 45% sodium carbonate: 25% caustic soda: 8% N
2H
4H
2O:1%
All the other 21% are water and other trace impurity.
Embodiment 1: above-mentioned saline and alkaline mixture is handled as follows:
(a) the slurrying step adopts hot water to carry out slurrying as the slurrying medium: be evacuated to 90 ℃ of hot water of discharging in the system in the pulping tank of band stirring with pump, open to stir and successively add hydrazine hydrate by-product saline-alkali mixture, made solid-to-liquid ratio and be 0.8: 1 and contained the supersaturation slurries of sodium carbonate, sodium chloride, caustic soda, hydrazine hydrate;
(b) separating step of salt slurry and alkali slurry: with pump the slurries that make in (a) step are squeezed into the suspension device and carry out classification, utilize the gravity different principle of salt slurry and alkali slurry that the salt slurry is separated with the alkali slurry, obtaining solid-to-liquid ratio respectively is 1: 1 salt slurry and 0.6: 1 alkali slurry;
(c) treatment step of salt slurry: contain following material in the mother liquor that the salt slurry that classification in (b) step is gone out obtains after centrifuge separates: content is the caustic soda of 50g/l, content is the sodium chloride of 200g/l, content is the sodium carbonate of 100g/l, content is the hydrazine hydrate of 5g/l, contain 8% caustic soda and 85% sodium chloride in the centrifugal solid sodium chloride that obtains, this solid sodium chloride is configured to solution through adding water, add hydrochloric acid neutralization caustic soda wherein again, adjusting pH value is 8～9, being mixed with sodium chloride content is 250g/l, the refined brine of total ammonium content≤80ppm send the chlor-alkali system as the raw material of producing chlorine and caustic soda this refined brine.
(d) treatment step of alkali slurry: alkali slurry that will classification goes out in (b) step obtains carbonate content after the centrifuge separation be 65% monohydrated sodium carbonate and mother liquor, this monohydrated sodium carbonate sent in the rotary kiln under 500 ℃ of conditions calcine, calcination time was controlled at 1 hour, remove the moisture in the monohydrated sodium carbonate, obtain sodium carbonate through pulverizing behind caustic soda and other impurity, to calcine the tail gas that produces simultaneously absorbs with water circulation in the air exhauster suction absorption tower, tail gas absorbs the back emptying, the absorption liquid that produces in the absorption tower send the sewage disposal collecting pit to handle through clear liquid behind the clarification filtration, and the water retrieval system of handling after qualified recycles;
(e) mother liquor reuse slurrying step: two kinds of mother liquors that produce in the treatment step with the treatment step of salt slurry and alkali slurry separate the back remittance together by centrifuge, keeping delivering to the slurrying step under 80 ℃ of conditions, continuation as next time saline and alkaline mixture the slurrying medium and recycle, under stirring condition, in mother liquor, add saline and alkaline, when the solid-to-liquid ratio of slurries at 0.8: 1, temperature configures slurries when being 90 ℃, no longer again, use hot water slurrying this moment, through behind the circulating pulp-making repeatedly, hydrazine hydrate in saline and alkaline and caustic soda constantly dissolve in the mother liquor, hydrazine hydrate content rises to 15g/l in mother liquor, when caustic soda content rises to 120g/l, with pump this mother liquor is returned vapo(u)rization system and distillation system and adopt that the conventional method evaporation is smart stays recovery hydrazine hydrate wherein, and the caustic soda that constantly consumes in the additional vapo(u)rization system.The mother liquor amount that reduces is replenished by the hot water that adds again, and mode of operation is the same.
Embodiment 2: prepare hydrazine hydrate according to above-mentioned conventional steps, the chemical analysis of the saline and alkaline mixture that obtains after the hydrazine hydrate in the thick solution with hydrazine hydrate, the water evaporation is as follows:
Sodium chloride: 30% sodium carbonate: 15% caustic soda: 10% N
2H
4H
2O:0.4%
All the other are water and other trace impurity.Above-mentioned saline and alkaline mixture is handled as follows:
(a) slurrying step: carry out slurrying as the slurrying medium: be evacuated to 65 ℃ of hot water of discharging in the system in the pulping tank of band stirring with pump with hot water, open to stir and successively add hydrazine hydrate by-product saline-alkali mixture, made solid-to-liquid ratio and be 0.3: 1 and contained the supersaturation slurries of sodium carbonate, sodium chloride, caustic soda, hydrazine hydrate;
(b) separating step of salt slurry and alkali slurry: with pump the slurries that make in (a) step are squeezed into the suspension device and carry out classification, utilize the gravity different principle of salt slurry and alkali slurry that the salt slurry is separated with the alkali slurry, obtaining solid-to-liquid ratio respectively is 0.6: 1 salt slurry and 0.3: 1 alkali slurry;
(c) treatment step of salt slurry: contain following material after the centrifuge separation in the mother liquor that salt slurry that will classification goes out in (b) step obtains: content is that sodium carbonate, the content that the caustic soda of 40g/l, solid sodium chloride that content is 150g/l and content are 80g/l is the hydrazine hydrate of 3g/l, the centrifugal solid sodium chloride that obtains is configured to solution, adds hydrochloric acid neutralization caustic soda wherein again through adding water, adjusting pH value is 8～9, being mixed with sodium chloride content is the refined brine of 250g/l, total ammonium content≤80ppm, send the chlor-alkali system as the raw material of producing chlorine and caustic soda this refined brine.
(d) treatment step of alkali slurry: alkali slurry that will classification goes out in (b) step obtains carbonate content after the centrifuge separation be 45% monohydrated sodium carbonate and mother liquor, this monohydrated sodium carbonate sent in the rotary kiln under 150 ℃ of conditions calcine, calcination time was controlled at 5 hours, remove the moisture in the monohydrated sodium carbonate, obtain sodium carbonate through pulverizing behind caustic soda and other impurity, to calcine the tail gas that produces simultaneously absorbs with water circulated in countercurrent in the air exhauster suction absorption tower, tail gas absorbs the back emptying, the absorption liquid that produces in the absorption tower send the sewage disposal collecting pit to handle through clear liquid behind the clarification filtration, and the water retrieval system of handling after qualified recycles;
(e) mother liquor reuse slurrying step: two kinds of mother liquors that produce in the treatment step with the treatment step of salt slurry and alkali slurry separate the back remittance together by centrifuge, keeping delivering to the slurrying step under 60 ℃ of conditions, continuation as next time saline and alkaline mixture the slurrying medium and recycle, under stirring condition, in mother liquor, add saline and alkaline, when the solid-to-liquid ratio of slurries at 0.3: 1, temperature configures slurries when being 80 ℃, no longer again, use hot water slurrying this moment, through behind the circulating pulp-making repeatedly, hydrazine hydrate in saline and alkaline and caustic soda constantly dissolve in the mother liquor, hydrazine hydrate content rises to 6g/l in mother liquor, when caustic soda content rises to 60g/l, with pump this mother liquor is returned vapo(u)rization system and distillation system and adopt that the conventional method evaporation is smart stays recovery hydrazine hydrate wherein, and the caustic soda that constantly consumes in the additional vapo(u)rization system.The mother liquor amount that reduces is replenished by the hot water that adds again, and mode of operation is the same.
Claims (1)
1. a recovering treatment of hydrated hydrazine by-product saline-alkali by urea method comprises the steps:
(a) slurrying step: by-product saline-alkali in the urea method hydrazine hydrate reaction under stirring condition, is added temperature in 65-90 ℃ hot water, make solid-to-liquid ratio and be 0.3～0.8: 1 the slurries that contain sodium carbonate, sodium chloride, caustic soda, hydrazine hydrate;
(b) separating step of salt slurry and alkali slurry: (a) salt slurry that mainly contains sodium chloride and the alkali slurry that mainly contains sodium carbonate are arranged in the slurries that make in the step, utilize the gravity different mining of salt slurry and alkali slurry with classifying equipoment the salt slurry to be separated with the alkali slurry, obtaining solid-to-liquid ratio respectively is 0.6-1: 1 salt slurry and 0.3-0.6: 1 alkali slurry;
(c) treatment step of salt slurry: will be in (b) step isolated salt slurry after the centrifuge separation, obtain caustic soda content be 2～8% and sodium chloride content be 65～85% solid sodium chloride and mother liquor, the solid sodium chloride that obtains is configured to solution, adds between acid adjustment its pH value to 8～9 through adding water, being mixed with sodium chloride content is the refined brine of 200～300g/l, total ammonium content≤80ppm, send the chlor-alkali system as the raw material of producing chlorine and caustic soda this refined brine;
(d) treatment step of alkali slurry: will be in (b) step isolated alkali slurry to obtain carbonate content after the centrifuge separation be 45～65% monohydrated sodium carbonate and mother liquor, this monohydrated sodium carbonate sent in the rotary kiln under 150～500 ℃ of conditions calcine, calcination time was controlled at 1～5 hour, remove the moisture in the monohydrated sodium carbonate, obtain sodium carbonate through pulverizing behind caustic soda and other impurity, to calcine the tail gas that produces simultaneously absorbs with water circulation in the air exhauster suction absorption tower, tail gas absorbs the back emptying, and the absorption liquid that produces in the absorption tower send the sewage disposal collecting pit through behind the clarification filtration;
(e) mother liquor reuse slurrying step: two kinds of mother liquors that produce in the treatment step with the treatment step of (c) salt slurry and (d) alkali slurry separate remittance afterwards together by centrifuge, keeping delivering to the slurrying step under 60～90 ℃ of conditions, continuation as next time saline and alkaline mixture the slurrying medium and recycle, under stirring condition, in mother liquor, add by-product saline-alkali, when the solid-to-liquid ratio of slurries 0.3～0.8: 1, temperature configures slurries when being 80～95 ℃, through behind the circulating pulp-making repeatedly, hydrazine hydrate in saline and alkaline and caustic soda constantly dissolve in the mother liquor, hydrazine hydrate rises to 5～15g/l in mother liquor, when caustic soda rises to 60～120g/l, with pump this mother liquor is returned vapo(u)rization system recovery hydrazine hydrate wherein, and the caustic soda that constantly consumes in the additional vapo(u)rization system.
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| CN101219973B (en) * | 2008-01-22 | 2010-06-02 | 浙江海虹控股集团有限公司 | Process for producing biurea |
| CN101786643B (en) * | 2010-03-18 | 2011-08-31 | 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 |
| CN103896808A (en) * | 2014-04-12 | 2014-07-02 | 唐山晨虹实业有限公司 | Method of preparing azodiisobutyronitrile |
| CN109534361B (en) * | 2018-12-19 | 2021-03-09 | 青海盐湖工业股份有限公司 | Method for purifying sodium chloride from byproduct mixed salt |
| CN111498910B (en) * | 2020-05-26 | 2022-09-16 | 宜宾海丰和锐有限公司 | Resource utilization method of chlorination waste residue |
| CN112250049B (en) * | 2020-09-24 | 2023-06-20 | 江苏索普化工股份有限公司 | Separation method of hydrazine hydrate byproduct saline-alkali by urea method |
| CN115350500B (en) * | 2022-08-23 | 2023-10-13 | 宁夏日盛高新产业股份有限公司 | Byproduct comprehensive utilization system in foaming agent production |
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| CN1046328A (en) * | 1989-04-13 | 1990-10-24 | 成都华西化工研究所 | Alkali cycling process with production of hydrated hydrazine from urea |
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| CN1274685A (en) * | 2000-05-25 | 2000-11-29 | 赖中胜 | Method for denirifying from hydrazine hydrate salt mud |
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| CN1046328A (en) * | 1989-04-13 | 1990-10-24 | 成都华西化工研究所 | Alkali cycling process with production of hydrated hydrazine from urea |
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