CN1034349A - The recovery method of ammonium thiocyanate - Google Patents

The recovery method of ammonium thiocyanate Download PDF

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Publication number
CN1034349A
CN1034349A CN 88105463 CN88105463A CN1034349A CN 1034349 A CN1034349 A CN 1034349A CN 88105463 CN88105463 CN 88105463 CN 88105463 A CN88105463 A CN 88105463A CN 1034349 A CN1034349 A CN 1034349A
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cns
washing
described recovery
liquid
technology
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CN 88105463
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CN1014230B (en
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戴开义
郁正容
戴兰芳
曹霞芳
丁炳顺
卢武胜
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SHANGHAI CHEMICAL ENGINEERING DESIGN INST
Shanghai Research Institute of Chemical Industry SRICI
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SHANGHAI CHEMICAL ENGINEERING DESIGN INST
Shanghai Research Institute of Chemical Industry SRICI
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Abstract

The present invention is the principle of utilization multicomponent system aqueous phase diagram, directly separates NH in the processes of coke oven gas desulfurization and decyanation waste water for solving 4The method of CNS provides reliable recovery technology, has improved NH 4The purity of CNS.The NH that the present invention reclaims 4CNS undried content can reach more than 95% (weight), dry rear NH 4CNS can reach more than 99% (weight).The intermediate and the printing and dyeing auxiliary that can be used for synthetic organic pesticide.It is simple to have technology, and technology is novel reliable, advanced practical, characteristics with low cost.The present invention has successfully solved the pollution of coke(oven)gas decyanation waste water to environment, and has made full use of the effective chemical energy in the coke(oven)gas.

Description

The recovery method of ammonium thiocyanate
The present invention belongs to ammonium thiocyanate (NH from processes of coke oven gas desulfurization and decyanation waste water 4CNS) recovery technology.
In prior art, the recovery method of ammonium thiocyanate is a lot of in the processes of coke oven gas desulfurization and decyanation waste water.Japan Patent examined patent publication 57-7825 thinks that the wastewater for desulfurization and decyanation of Fumaks method is owing to contain ATS (Ammonium thiosulphate) ((NH 4) 2S 2O 3) ratio higher, it and NH 4The solubility of CNS in water is all very big, can't utilize the difference of solubility to be separated.Therefore propose decolouring waste water and join ammonia, make catalyzer with copper sulfate, in autoclave with (NH 4) 2S 2O 3Change into ammonium sulfate ((NH 4) 2SO 4) (150～155 ℃, 1～5 kilograms per centimeter 2), remove cupric ion through ion exchange resin then, contain NH 4CNS and (NH 4) 2SO 4Aqueous solution concentration and evaporation, tell solid phase (NH under the hot state 4) 2SO 4, the liquid phase cools crystallization goes out NH 4CNS.This method operation steps is many, and will carry out in pressurized vessel.Though the special public clear 57-17421 of Japanese Patent to the technology of the special public clear 57-7825 of Japanese Patent done one this revise, remove (NH at the solution evaporation branch of wet oxidation 4) 2SO 4After solution need add calcium hydroxide (Ca(OH) 2), to remove the SO in the solution -2 4, could improve NH 4The quality of CNS.Japan Patent examined patent publication 57-156325 confirms NH 4CNS and (NH 4) 2S 2O 3Separation very difficult, and NH 4CNS and (NH 4) 2SO 4Separation be feasible, (NH in waste water 4) 2S 2O 3Content be NH 4Below 1/2 of CNS content is although can obtain 97%(weight) above dry product NH 4CNS, but from the example of this patent NH as can be known 4The rate of recovery of CNS＜40%.Do not mention (NH in the patent 4) 2S 2O 3Tell, and extract NH 4Mother liquor behind the CNS can't be processed, its (NH 4) 2S 2O 3Content inevitable raise because of accumulation.Cause and to continue to reclaim NH 4CNS, so the technology of this patent still can't suitability for industrialized production.So up to the present still there is not (NH in the easy solution waste water 4) 2S 2O 3/ NH 4The CNS(weight ratio) up to 1.1 separation method.
The objective of the invention is to solve (NH in oven gas wet desulphurization decyanation waste water 4) 2S 2O 3/ NH 4The CNS(weight ratio) up to 1.1 o'clock, can be economical and effectively isolate solid phase (NH 4) 2S 2O 3With solid phase NH 4The method of CNS, NH 4The purity of CNS meets the requirement of commercial Application.
Design of the present invention is to be main component NH 4CNS, (NH 4) 2S 2O 3, (NH 4) 2SO 4, H 2The processes of coke oven gas desulfurization and decyanation waste water of O mixes with circulating mother liquor after Tuo Se And drives away volatizable material, forms multicomponent system.Use the principle of multicomponent system aqueous phase diagram, multicomponent system is simplified to NH 4CNS-(NH 4) 2S 2O 3-H 2The O ternary system.When waste water process decolorization filtering, And isothermal reduction vaporization under specific temperature concentrates.The general evaporation concentration whole process of finishing under lower temperature and in the short time is for well.Vaporization temperature can be at 50～95 ℃, and for fear of the decomposition of some component, best concentrated condition is: vacuum tightness 〉=700 mmhg, liquidus temperature are 65～80 ℃ in evaporating concentration process.The component of the concentrated rear liquid phase of process reduction vaporization will reach or near common saturation point, only have (NH this moment 4) 2S 2O 3Separate out, available centrifuge carries out liquid-solid separation.Liquid-solid isolating temperature generally is 30～80 ℃, and best liquid-solid isolating temperature is 42～57 ℃.The solid phase that obtains is (NH 4) 2S 2O 3, filtrate being contains on a small quantity (NH 4) 2S 2O 3NH 4CNS adds H 2The saturated liquid of O.If it is just bad not reach separating effect saturated altogether then system, NH 4The CNS yield will reduce.And (NH in the product 4) 2S 2O 3Content can increase.
After the liquid-solid separation, reach the common saturation point of this temperature in order to make cooling rear filtrate component, only have NH this moment 4CNS separates out, and need to add washing finished product NH in original filtrate 4The washing lotion of CNS, the component of washing lotion is to contain NH 4CNS, (NH 4) 2S 2O 3The aqueous solution.The consumption of washing lotion is original 1.0～50%(weight of saturated solution altogether), best washing lotion amount is original 3～25%(weight of saturated solution altogether).
Add the saturated liquid crystallisation by cooling after the washing lotion, make it enter NH 4The crystallizing field of CNS is separated out NH 4CNS, Tc is generally at-10～40 ℃, and best Tc is 10～35 ℃.Again through liquid-solid separation, solid phase is removed attached liquid through washing can contain NH behind the primary crystallization 4CNS 〉=95%(weight) product, dry rear NH 4CNS can reach 99%(weight) more than.Crystalline mother solution returns together reduction vaporization and concentrates and recycle, and washing lotion is returned cooling system.
The present invention reclaims NH to oven gas wet desulphurization decyanation waste water 4The technology of CNS has been done deep research, and the mother liquor of flow process inside, washing lotion have all been done rational arrangement, reaches the level of closed cycle.
Effect of the present invention is that processes of coke oven gas desulfurization and decyanation waste water reclaims technology a breakthrough is arranged, and can reclaim NH from the ammonium salt system 4CNS.The wet desulphurization decyanation technology is owing to can't directly reclaim NH from the ammonium salt system both at home and abroad 4CNS often is forced to adopt soda lye to absorb, and makes waste water become the sodium salt system, thus separate reclaim NaCNS.Therefore need a large amount of caustic soda, and the contained NH of oven gas itself 3Do not utilized, given again enrichment after going to desulfurization and decyanation technology.Recovery method of the present invention does not need external raw material can finish the requirement of desulfuration and decyanation, reduces simultaneously NH in the oven gas 3Recovery load.Therefore the present invention makes full use of the effective chemical energy in the coke(oven)gas, and And provides technical guarantee to the reform of wet desulphurization decyanation wastewater recycling process, has solved the pollution problem to environment.
The NH that the present invention obtained 4CNS can be used for the intermediate of synthetic organic pesticide, encircles (gram pest) azoles, bismerthlazol, printing and dyeing auxiliary and the conduct oil field tracer of exploitation recently as three.Domestic synthetic NH 4The cost of CNS is higher, thereby adopts NaCNS to replace doing the printing and dyeing assistant.The present invention reclaims NH from processes of coke oven gas desulfurization and decyanation waste water 4The cost of CNS reduces, and has only synthetic legal system NH 4Half of CNS is for dyeing industry provides cheap NH 4CNS.Technology of the present invention is simple, and technology is novel reliable, remarkable in economical benefits.
Accompanying drawing of the present invention is that the evaporation of decolouring waste water is anhydrated, the crystallisation by cooling phasor.
In Fig. 1, starting soln point 0, evaporation is anhydrated from H 2The O direction moves, and namely begins to have (NH behind the B point 4) 2S 2O 3Crystallization, the liquidus point that continues to anhydrate are then constantly separated out solid phase (NH along the BA line to A 4) 2S 2O 3The A point is the point of satisfying altogether.M is (NH 4) 2S 2O 3The solubility of one pack system, N is NH 4The solubility of CNS one pack system.
In Fig. 2, solid phase NH is separated out in the cooling of liquid phase A point 4CNS ， And obtains C point (altogether full point) solution.M ' is (NH when satisfying altogether some C corresponding temperature 4) 2S 2O 3The solubility of one pack system, N ' is the NH when satisfying altogether some C corresponding temperature 4The solubility of CNS one pack system.This is the most basic theoretical basis of the present invention.
Embodiments of the invention below.
Example 1: decolouring waste water 1000 gram ((NH 4) 2S 2O 320.37%; NH 4CNS 20.75%; (NH 4) 2SO 40.79%; H 2O58.09%), adds and to return mother liquor 1050 grams, in 55～70 ℃ of reduced pressure concentrations, 600 grams that anhydrate.Isolate solid phase 224 gram ((NH in 40～50 ℃ 4) 2S 2O 386.74%; NH 4CNS3.43%; (NH 4) 2SO 41.94%; H 2O7.89%), add 120 gram washing finished product NH in the liquid phase 4The washing lotion of CNS is cooled to 5～15 ℃, separate, wash product NH 4CNS176 restrains (NH 4CNS95%; (NH 4) 2S 2O 30.37%; (NH 4) 2SO 40.2%; H 2O4.4%), mother liquor 1050 grams return vapo(u)rization system, and washing lotion 120 grams return cooling system.
Example 2: decolouring waste water 2000 gram ((NH 4) 2S 2O 318.97%; NH 4CNS17.68%; (NH 4) 2SO 40.27%; H 2O63.13%), adds and to return mother liquor 2120 grams, in 75～90 ℃ of reduction vaporizations, 1300 grams that anhydrate, isolate solid phase 400 gram ((NH in 55～65 ℃ 4) 2S 2O 385.11%; NH 4CNS3.57%; (NH 4) 2SO 41.73%; N 2O9.59%), add washing NH in the liquid phase 4Washing lotion 240 gram of CNS is cooled to 25～35 ℃, separate, wash product NH 4CNS300 restrains (NH 4CNS95%; (NH 4) 2S 2O 30.4%; (NH 4) 2SO 40.2%; H 2O4.4%), mother liquor 2120 grams return vapo(u)rization system, and washing lotion 240 grams return cooling system.
Comparative Examples: the condition identical with example 2 only do not add washing NH in liquid phase 4The washing lotion of CNS.Separate product NH 4CNS330 restrains (NH 4CNS81.5%; (NH 4) 2S 2O 314.3%; (NH 4) 2SO 40.2%; H 2O 4.0%).

Claims (7)

1, a kind of recovery technology of ammonium thiocyanate, feature of the present invention is: use the principle of multicomponent system aqueous phase diagram, the waste water of processes of coke oven gas desulfurization and decyanation through decolour, mix with circulating mother liquor, reduction vaporization concentrates, make (NH 4) 2S 2O 3Be solid separation, obtain saturated liquid after the liquid-solid separation, add washing finished product NH then 4The washing lotion of CNS, crystallisation by cooling, again through liquid-solid separation, Recycling Mother Solution use, solid phase removes attached liquid through washing, improves the purity of ammonium thiocyanate.
2, according to the described recovery technology of claim 1, it is characterized in that: multicomponent system is meant (NH 4) S 2O 3-NH 4CNS-H 2O.
3, according to claim 1,2 described recovery technologies is characterized in that: multicomponent system is common saturated solution.
4, according to the described recovery technology of claim 1, it is characterized in that: (NH 4) 2S 2O 3The separation temperature that is solid separation is 30～80 ℃, and best separation temperature is 42～57 ℃.
5, according to the described recovery technology of claim 1, it is characterized in that: add washing finished product NH 4The washing lotion of CNS is to adjust to divide (NH 4) 2S 2O 3Common saturated solution to NH 4The CNS crystal region.
6, according to claim 1,5 described recovery technologies is characterized in that: washing finished product NH 4The washing lotion amount of CNS is 1.0～50%(weight of common saturated solution amount), best washing lotion amount is 3～25%(weight of common saturated solution amount).
7, according to the described recovery technology of claim 1, it is characterized in that: the temperature of crystallisation by cooling is-10～40 ℃, and the temperature of best crystallisation by cooling is 10～35 ℃.
CN 88105463 1988-01-21 1988-01-21 Recovery of ammonium thyiocyanate Expired CN1014230B (en)

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CN 88105463 CN1014230B (en) 1988-01-21 1988-01-21 Recovery of ammonium thyiocyanate

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CN 88105463 CN1014230B (en) 1988-01-21 1988-01-21 Recovery of ammonium thyiocyanate

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CN1014230B CN1014230B (en) 1991-10-09

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101823730A (en) * 2010-05-25 2010-09-08 安徽工业大学 Method for simultaneously producing sodium thiocyanate and ammonium carbonate
CN101143744B (en) * 2006-09-13 2010-12-01 苏州市浒关焦炉煤气三废治理厂 Reclamation of ammonium sulfocyanate and ammonium thiosulfate from coke oven gas ammonia liquid phase catalysis waste water
CN103864115A (en) * 2014-03-10 2014-06-18 宜兴市燎原化工有限公司 Method of producing ammonium thiocyanate by using crude product ammonium thiocyanate recovered from waste liquid

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101143744B (en) * 2006-09-13 2010-12-01 苏州市浒关焦炉煤气三废治理厂 Reclamation of ammonium sulfocyanate and ammonium thiosulfate from coke oven gas ammonia liquid phase catalysis waste water
CN101823730A (en) * 2010-05-25 2010-09-08 安徽工业大学 Method for simultaneously producing sodium thiocyanate and ammonium carbonate
CN103864115A (en) * 2014-03-10 2014-06-18 宜兴市燎原化工有限公司 Method of producing ammonium thiocyanate by using crude product ammonium thiocyanate recovered from waste liquid
CN103864115B (en) * 2014-03-10 2016-05-04 江苏燎原环保科技股份有限公司 The method that waste liquid reclaims crude product ammonium thiocyanate produces ammonium thiocyanate

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