CN108342681A - A kind of environment-friendly type nitridation salt and its preparation method and application for QPQ techniques - Google Patents
A kind of environment-friendly type nitridation salt and its preparation method and application for QPQ techniques Download PDFInfo
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- CN108342681A CN108342681A CN201810108419.7A CN201810108419A CN108342681A CN 108342681 A CN108342681 A CN 108342681A CN 201810108419 A CN201810108419 A CN 201810108419A CN 108342681 A CN108342681 A CN 108342681A
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- 150000003839 salts Chemical class 0.000 title claims abstract description 182
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims abstract description 44
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 41
- 229910000027 potassium carbonate Inorganic materials 0.000 claims abstract description 33
- 229910052808 lithium carbonate Inorganic materials 0.000 claims abstract description 32
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 31
- 229910052938 sodium sulfate Inorganic materials 0.000 claims abstract description 31
- LIXWSNVLHFNXAJ-UHFFFAOYSA-N sodium;oxidoazaniumylidynemethane Chemical compound [Na+].[O-][N+]#[C-] LIXWSNVLHFNXAJ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000007832 Na2SO4 Substances 0.000 claims abstract description 28
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Substances [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 28
- 238000002844 melting Methods 0.000 claims abstract description 27
- 230000008018 melting Effects 0.000 claims abstract description 27
- 239000001103 potassium chloride Substances 0.000 claims abstract description 23
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims abstract description 15
- ZVCDLGYNFYZZOK-UHFFFAOYSA-M sodium cyanate Chemical compound [Na]OC#N ZVCDLGYNFYZZOK-UHFFFAOYSA-M 0.000 claims abstract description 12
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims abstract description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims abstract description 4
- -1 KCNO Chemical compound 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 238000003723 Smelting Methods 0.000 claims description 8
- 239000000654 additive Substances 0.000 claims description 6
- 230000000996 additive effect Effects 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 4
- 238000004806 packaging method and process Methods 0.000 claims description 4
- 238000012856 packing Methods 0.000 claims description 4
- 238000003860 storage Methods 0.000 claims description 4
- 235000015320 potassium carbonate Nutrition 0.000 claims 1
- 235000017550 sodium carbonate Nutrition 0.000 claims 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 30
- 229910021529 ammonia Inorganic materials 0.000 abstract description 15
- 238000005121 nitriding Methods 0.000 abstract description 13
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 231100000252 nontoxic Toxicity 0.000 abstract description 6
- 230000003000 nontoxic effect Effects 0.000 abstract description 6
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- 230000001590 oxidative effect Effects 0.000 abstract description 5
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 3
- 239000000428 dust Substances 0.000 abstract description 3
- 238000007499 fusion processing Methods 0.000 abstract description 3
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 18
- 239000000203 mixture Substances 0.000 description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 11
- 239000004202 carbamide Substances 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 11
- 239000004615 ingredient Substances 0.000 description 11
- XLJMAIOERFSOGZ-UHFFFAOYSA-N anhydrous cyanic acid Natural products OC#N XLJMAIOERFSOGZ-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 229910001414 potassium ion Inorganic materials 0.000 description 8
- 239000007789 gas Substances 0.000 description 6
- 125000004430 oxygen atom Chemical group O* 0.000 description 6
- BITYAPCSNKJESK-UHFFFAOYSA-N potassiosodium Chemical compound [Na].[K] BITYAPCSNKJESK-UHFFFAOYSA-N 0.000 description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 229910052700 potassium Inorganic materials 0.000 description 5
- 239000011591 potassium Substances 0.000 description 5
- 239000011734 sodium Substances 0.000 description 5
- 150000002500 ions Chemical class 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052761 rare earth metal Inorganic materials 0.000 description 3
- 150000002910 rare earth metals Chemical class 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000003381 stabilizer Substances 0.000 description 3
- 231100000331 toxic Toxicity 0.000 description 3
- 230000002588 toxic effect Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 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 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- NPYPAHLBTDXSSS-UHFFFAOYSA-N Potassium ion Chemical compound [K+] NPYPAHLBTDXSSS-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- PNEFIWYZWIQKEK-UHFFFAOYSA-N carbonic acid;lithium Chemical compound [Li].OC(O)=O PNEFIWYZWIQKEK-UHFFFAOYSA-N 0.000 description 2
- 238000000205 computational method Methods 0.000 description 2
- 239000011162 core material Substances 0.000 description 2
- 239000013039 cover film Substances 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000012492 regenerant Chemical class 0.000 description 2
- 231100000004 severe toxicity Toxicity 0.000 description 2
- 239000011780 sodium chloride Substances 0.000 description 2
- 238000010257 thawing Methods 0.000 description 2
- 231100000167 toxic agent Toxicity 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 1
- 229910017569 La2(CO3)3 Inorganic materials 0.000 description 1
- XTIMETPJOMYPHC-UHFFFAOYSA-M beryllium monohydroxide Chemical compound O[Be] XTIMETPJOMYPHC-UHFFFAOYSA-M 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- VXCSPBPIGBJXJR-UHFFFAOYSA-N cyanic acid;sodium Chemical compound [Na].OC#N VXCSPBPIGBJXJR-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910001337 iron nitride Inorganic materials 0.000 description 1
- 230000000622 irritating effect Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 150000002829 nitrogen Chemical class 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C8/00—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C8/40—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions
- C23C8/42—Solid state diffusion of only non-metal elements into metallic material surfaces; Chemical surface treatment of metallic material by reaction of the surface with a reactive gas, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using liquids, e.g. salt baths, liquid suspensions only one element being applied
- C23C8/48—Nitriding
- C23C8/50—Nitriding of ferrous surfaces
Abstract
The environment-friendly type nitridation salt and its preparation method and application that the invention discloses a kind of for QPQ techniques, it is as the main component with Zassol, it is characterised in that：By mass, including following each component NaCNO 35% 55%, KCNO 0% 20%, Na2CO3 5% 10%, K2CO3 15% ~ 35%, KCl 0% 15%, KOH 0% 10%, Li2CO3 0% 5%, Na2SO4 0%‑2%.The nitridation salt is as the main component with Zassol, using carbonate as fused-salt medium, using sodium sulphate as oxidant, using chloride as energizer, have nitriding speed fast, the wide feature of proper temperature range, it is crucial that, this formula nitridation salt not will produce ammonia release in fusion process, nontoxic and pollution-free, in melting production process, it is few with dust, it is a kind of environment-friendly type nitridation salt the characteristics of the release of no ammonia.
Description
Technical field
The invention belongs to nitridation salt manufacturing technology field more particularly to a kind of environment-friendly type nitridation salt for QPQ techniques and
Preparation method and application.
Background technology
QPQ art process technologies are a kind of bath nitriding technologies, and it is former to provide active nitrogen using the nitridation salt under molten condition
Sub [N] penetrates into fe-based surface, forms the iron nitride of hard and compact, so as to increase substantially iron-based material wearability and
Corrosion stability.The technology initially enters China from the nineties, quickly grows, and is had developed at home at present in order to a kind of extensive
Application, basic ferrous metals process of surface treatment.
The core of QPQ technologies is to be its technique salt bath.QPQ salt baths are made of three parts, are nitridation salt, regenerant salt respectively
And saline oxide.Nitridation salt provides nitridation salt bath media base, and saline oxide provides oxidation salt bath media base, and regenerant salt is for adjusting
Nitriding activity that is whole, restoring nitridation salt bath.Nitridation salt is the core material of QPQ techniques, and outstanding nitridation salt formula is not only only capable of
Meet the physical and chemical index demand of product, but also should be environment friendly and pollution-free.
Traditional QPQ nitridation salts are as the main component with urea, remix other ingredients such as sodium carbonate, mix in proportion and
At.The nitridation salt advantage of this ingredient is that cost is very low；The disadvantage is that needing to release during melting or use a large amount of
Ammonia, seriously pollute environment.
The nitridation salt of the conventional urea type reaction principle that ammonia discharges in melting is as follows：
As shown in above-mentioned reaction equation, in urea type nitridation salt, urea and sodium carbonate reaction generate Zassol, together
When discharge a large amount of ammonias, carbon dioxide.By the formula estimation for the urea type nitridation salt that currently available technology is announced out, every 1 is public
Jin urea type nitridation salt can discharge 0.2 cubic metre of ammonia when melting produces, by annual 10000 tons of the urea type nitridation salt of China
Usage amount estimates that the ammonia total amount that then China discharges because melting produces urea type nitridation salt every year is：200 ten thousand steres, foot
To generate huge pollution to environment.
Number of patent application provides a kind of rare earth for deep layer QPQ technologies and matches for 201510894920.7 patent of invention
Square salt and preparation method thereof, the rare earth formula salt for deep layer QPQ technologies are made of the raw material of following weight parts：30‐50
Part CO (NH2)2, 10-30 parts of K2CO3, 10-30 parts of Na2CO3, 5-15 parts of NH4Cl, 1-5 parts of K2SO3, 1-5 parts of La2(CO3)3, 3-7
Part BeOH.Rare earth formula salt used in the invention is also that will produce a large amount of ammonia in use using urea as primary raw material
Gas pollutes environment.
Invention content
In order to overcome ammonia pollution problem of the current urea type QPQ nitridation salts in melting production process, the present invention to provide
A kind of environment-friendly type nitridation salt for QPQ techniques, the nitridation salt is as the main component with Zassol, using carbonate as fused-salt medium,
Using sodium sulphate as oxidant, using chloride as energizer, have nitriding speed fast, the wide feature of proper temperature range, most critical
, this formula nitridation salt not will produce ammonia release in fusion process, nontoxic and pollution-free, in melting production process, tool
There is the characteristics of dust is few, no ammonia release, is a kind of environment-friendly type nitridation salt.
A kind of environment-friendly type nitridation salt for QPQ techniques, it is as the main component with Zassol, by mass, including it is following
Component NaCNO 35%-55%, KCNO 0%-20%, Na2CO35%-10%, K2CO315%~35%, KCl 0%-
15%, KOH 0%-10%, Li2CO30%-5%, Na2SO40%-2%.
Under the formula, it is desirable that：
1, sodium potassium ion ratio【Na+】:【K+】Between：4:6 to 6:Between 4.
2, cyanic acid ion concentration【CNO-】Between：Between 30~37%.
Including following each component NaCNO 40%-50%, KCNO 5%-10%, Na preferably, by mass,2CO3
5%-10%, K2CO320%~30%, KCl 5%-10%, KOH 0%-10%, Li2CO32.5%-5%, Na2SO4
0.5%-2%.
In any of the above-described scheme preferably, under the formula, sodium potassium ion ratio【Na+】:【K+】Between 4:6 to 6:4 it
Between.
In any of the above-described scheme preferably, under the formula, cyanic acid ion concentration【CNO-】Between 30~37% it
Between.
It is preferably in any of the above-described scheme, by mass, including following each component NaCNO 55%, Na2CO35%,
K2CO315%, KCl 10%, KOH 10%, Li2CO34.5%, Na2SO40.5%.
It is preferably in any of the above-described scheme, by mass, including following each component NaCNO 50%, KCNO 5%,
Na2CO35%, K2CO320%, KCl 10%, KOH 5%, Li2CO34%, Na2SO41%.
It is preferably in any of the above-described scheme, by mass, including following each component NaCNO 45%, KCNO 10%,
Na2CO37%, K2CO335%, Li2CO32.5%, Na2SO40.5%.
It is preferably in any of the above-described scheme, by mass, including following each component NaCNO 40%, KCNO 15%,
Na2CO37%, K2CO330%, KCl 5%, Li2CO32.5%, Na2SO40.5%.
It is preferably in any of the above-described scheme, by mass, including following each component NaCNO 35%, KCNO 20%,
Na2CO310%, K2CO320%, KCl 5%, KOH 5%, Li2CO33%, Na2SO42%.
The present invention also provides a kind of preparation methods of the environment-friendly type nitridation salt for QPQ techniques, include the following steps：
(1) is prepared：By NaCNO, KCNO, Na2CO3, K2CO3, KCl, KOH, Li2CO3, Na2SO4It is equal by formula rate mixing
It is even；
(2) melting：Prepared raw material salt is put into melting in crucible furnace；
(3) scoops salt cooling：The nitridation salt molten liquid of smelting completion is scooped out and pours into cooled and solidified in cooler pan；
(4) is packed：Nitridation salt after cooling is packaged into the finished product packing bag of customization, packaging and storage.
In any of the above-described scheme preferably, in the step (2) smelting temperature be 600 DEG C~630 DEG C, the time be 9~
16 hours.
In any of the above-described scheme preferably, cooling time is 5~10 hours in the step (3), is cooled to room temperature.
The present invention also provides a kind of application processes of the above-mentioned environment-friendly type nitridation salt for QPQ techniques, include the following steps：
(1) additive amount of nitridation salt is calculated by volume and density；
(2) nitridation salt is added under the conditions of nitrogenizing salt temperature；
In any of the above-described scheme preferably, nitridation salt density is 2100 kilograms per cubic meter in step (1).
In any of the above-described scheme preferably, ranging from 500 DEG C -630 DEG C of salt temperature is nitrogenized in step (2).
In any of the above-described scheme preferably, nitridation salt is added to nitridation salt by the way of directly adding in step (2)
In bath.
The effect of each component of the present invention and reaction principle are as follows：
1, NaCNO and KCNO is the basic ingredient of nitridation salt, for providing the cyanic acid ion in nitridation salt【CNO-】, it
Afterwards again by cyanic acid ion【CNO-】Decomposite activated nitrogen atom【N】, nitrogen gesture is provided for salt bath, to achieve the purpose that nitriding.
Its reaction equation is as follows：
2、Na2CO3And K2CO3For the fused-salt medium ingredient of nitridation salt, the two mixing thawing on the one hand can balance and salt bath
Sodium potassium ion ratio, on the other hand can reduce the molten point of fused salt mixt, a suitable nitriding temperature area is provided for nitriding
Between.
3, KOH potassium contents are high, at low cost, can be used as and promote nitridation salt potassium concentration, balance nitridation salt sodium potassium ion
The efficient ingredient of ratio.
4, KCL is one of the fused-salt medium ingredient of nitridation salt, and one side potassium ion can be used for balancing the sodium of nitridation salt bath
Potassium concentration, another aspect Cl ions can be played certain urging to nitriding and oozed work with the cover film of corrosion dissolution metal surface
With.
5、Li2CO3It is the stabilizer for nitrogenizing salt bath, for expanding the proper temperature range of nitridation salt.Li2CO3It on the one hand can
To improve the stability of nitridation salt bath under the high temperature conditions, the fusing point of nitridation salt bath on the other hand can be reduced, is further increased
The mobility of salt bath at low temperature.Rational carbonic acid lithium content can significantly improve the stability of nitridation salt.
6、Na2SO4It is oxidant composition, plays the cyanide ion concentration inhibited in nitridation salt bath, reduce the work of salt bath toxicity
With.Its mechanism is：Cyanic acid ion meeting automatic classifying goes out toxic substance cyanide ion in nitridation salt bath【CN-】, and sulfate radical from
Sub- SO42-Meeting automatic classifying goes out active oxygen atom in salt bath, and active oxygen atom will be reacted with the cyanide ion in salt bath, again
Cyanic acid ion is generated, to play removal toxic component cyanide ion【CN-】Effect.It is intrinsic that QPQ techniques nitrogenize salt bath
One of environmental hazard be exactly salt bath itself can automatic classifying go out severe toxicity cyanide ion, some mechanisms provide QPQ Nacls exist
During use, salt bath cyanide ion content can be up to 6%-7%, even as high as 10%, this has huge environmental risk.
The Na of the present invention2SO4Composition can ensure that the cyanide ion concentration in nitridation salt bath is in micro content, to ensure that nitridation salt
Bath in use nontoxic.
Its reaction equation is as follows：
Nitridation salt bath cyanate radical decomposites toxic cyanide ion：
Nitridation salt sulfate ion decomposites active oxygen atom：
Cyanogen root is by active oxygen atom oxidation consumption
Sulfate ion【SO4 2-】Decomposition in nitrogenizing salt bath slowly carries out, in actual use with nitridation salt
Continuous consumption and new salt continuous addition, can be the sulfate ion in salt bath【SO4 2-】Always maintain one it is lower
Under levels, so that it is guaranteed that nitrogenizing salt bath cyanide ion in process of production【CN-】Content is under micro state always.
Advantageous effect
The present invention provides a kind of environment-friendly type nitridation salt for QPQ techniques, which is main with Zassol, potassium carbonate
Composition, nontoxic and pollution-free, in use, which has the advantages that in use：
(1) nitridation salt of the invention is in melting and in use, environmental protection is without exhaust emission, and nitridation salt of the invention is in melting
It is carried out without chemical reaction in journey, only the process of a fusing and ion mixing recombination, will not discharge ammonia between whole process
The irritative gas such as gas, it is free from environmental pollution, it is a kind of nitridation salt of environment-friendly type.This nitridation salt formula and urea type nitridation salt formula
It compares, using the nitridation salt of this formula per 1 kilogram of melting, then can reduce by 0.2 cubic metre of ammonia emission, by the annual melting of China
The amount of 10000 tons of nitriding furnaces estimates that then the present invention every year can reduce the ammonia emission total amount of 200 ten thousand steres.
(2) production melting is simple：The nitridation salt of the present invention does not chemically react progress, without exhaust gas when producing melting
Release, when producing melting, it is only necessary to which mixed melting need not handle exhaust gas, not need prolonged melting, and production is simple
It is easy.
(3) nitridation salt of the invention will can nitrogenize salt bath Poisoning composition automatically under the conditions of long-time service【CN‐】Ion
Content control at micro state (＜ ＜ 1%)：The nitridation salt of the present invention contains the composition for decomposing nitridation salt cyanide ion, can be with
Cyanide ion in automatic nitridation salt bath, to play the effect for ensuring that production process is environment-protecting and non-poisonous.
(4), it is good that stability is used for a long time：The nitridation salt of the present invention contains the ingredient of stable salt bath, Li2CO3It is nitridation salt bath
Stabilizer, be used for a long time stability it is good.
Specific implementation mode
In order to be best understood from technical scheme of the present invention and advantage, below by way of specific implementation mode, to the present invention do into
One step explanation.
Embodiment 1
A kind of environment-friendly type nitridation salt for QPQ techniques, it is as the main component with Zassol, by mass, optimization formula group
As NaCNO 50%, KCNO 5%, Na2CO35%, K2CO320%, KCl 10%, KOH 5%, Li2CO34%,
Na2SO41%.
In use, the effect of each component of the present invention and reaction principle are as follows：
The effect of each component of the present invention and reaction principle are as follows：
1, NaCNO and KCNO is the basic ingredient of nitridation salt, for providing the cyanic acid ion in nitridation salt【CNO-】, it
Afterwards again by cyanic acid ion【CNO-】Decomposite activated nitrogen atom【N】, nitrogen gesture is provided for salt bath, to achieve the purpose that nitriding.
Its reaction equation is as follows：
2、Na2CO3And K2CO3For the fused-salt medium ingredient of nitridation salt, the two mixing thawing on the one hand can balance and salt bath
Sodium potassium ion ratio, on the other hand can reduce the molten point of fused salt mixt, provide a night suitable nitriding temperature area for nitriding
Between.
3, KOH promotes the efficient ingredient of nitridation salt potassium content as balance nitridation salt sodium potassium ion ratio.
4, KCL is one of the fused-salt medium ingredient of nitridation salt, and one side potassium ion can be used for balancing the sodium of nitridation salt bath
Potassium concentration, another aspect Cl ions can be played certain urging to nitriding and oozed work with the cover film of corrosion dissolution metal surface
With.
5、Li2CO3It is the stabilizer for nitrogenizing salt bath, for expanding the proper temperature range of nitridation salt.Li2CO3It on the one hand can
To improve the stability of nitridation salt bath under the high temperature conditions, the fusing point of nitridation salt bath on the other hand can be reduced, is further increased
The mobility of salt bath at low temperature.Rational carbonic acid lithium content can significantly improve the stability of nitridation salt.
6、Na2SO4It is oxidant composition, plays the cyanide ion concentration inhibited in nitridation salt bath, reduce the work of salt bath toxicity
With.Its mechanism is：Cyanic acid ion meeting automatic classifying goes out toxic substance cyanide ion in nitridation salt bath【CN-】, and sulfate radical from
Sub- SO42-Meeting automatic classifying goes out active oxygen atom in salt bath, and active oxygen atom will be reacted with the cyanide ion in salt bath, again
Cyanic acid ion is generated, to play removal toxic component cyanide ion【CN-】Effect.It is intrinsic that QPQ techniques nitrogenize salt bath
One of environmental hazard be exactly salt bath itself can automatic classifying go out severe toxicity cyanide ion, some mechanisms provide QPQ Nacls exist
During use, salt bath cyanide ion content can be up to 6%-7%, even as high as 10%, this has huge environmental risk.
The Na of the present invention2SO4Composition can ensure that the cyanide ion concentration in nitridation salt bath is in micro content, to ensure that nitridation salt
Bath in use nontoxic.
The preparation method of the environment-friendly type nitridation salt of the present embodiment, includes the following steps：
(1) is prepared：By NaCNO, KCNO, Na2CO3, K2CO3, KCl, KOH, Li2CO3, Na2SO4It is equal by formula rate mixing
It is even；
(2) melting：Prepared raw material salt is put into melting in crucible furnace；
Smelting technology：630 DEG C of melting mixings 15 hours；
(3) scoops salt cooling：The nitridation salt molten liquid of smelting completion is scooped out and pours into cooler pan cooled and solidified to room
Temperature；
(4) it packs：Nitridation salt after cooling is packaged into the finished product packing bag of customization, packaging and storage.
The application process of the environment-friendly type nitridation salt of the present embodiment, includes the following steps：
(5) additive amount computational methods：The additive amount of nitridation salt is calculated by volume and density.This nitridation salt density is 2100
Kilograms per cubic meter.
(6) temperature is added：In nitridation salt temperature use can be added under from room temperature to 650 DEG C of temperature conditions.
(3) addition manner：This nitridation salt can be directly appended in nitridation salt bath.
Embodiment 2
A kind of environment-friendly type nitridation salt for QPQ techniques, as the main component with Zassol, by mass, formula composition is
NaCNO 35%, KCNO 20%, Na2CO310%, K2CO320%, KCl 5%, KOH 5%, Li2CO33%, Na2SO4
2%.
The preparation method of the environment-friendly type nitridation salt of the present embodiment, includes the following steps：
(1) is prepared：By NaCNO, KCNO, Na2CO3, K2CO3, KCl, KOH, Li2CO3, Na2SO4It is equal by formula rate mixing
It is even；
(2) melting：Prepared raw material salt is put into melting in crucible furnace.
Smelting technology：600 DEG C of melting mixings 9 hours；
(3) scoops salt cooling：The nitridation salt molten liquid of smelting completion is scooped out and pours into cooled and solidified in cooler pan.
(4) is packed：Nitridation salt after cooling is packaged into the finished product packing bag of customization, packaging and storage.
The application process of the environment-friendly type nitridation salt of the present embodiment, includes the following steps：
(1) additive amount computational methods：The additive amount of nitridation salt is calculated by volume and density.This nitridation salt density is 2100
Kilograms per cubic meter.
(2) temperature is added：In nitridation salt temperature use can be added under from room temperature to 650 DEG C of temperature conditions.
(3) addition manner：This nitridation salt can be directly appended in nitridation salt bath.
Embodiment 3
Unlike a kind of environment-friendly type nitridation salt and embodiment 1 for QPQ techniques, by mass, formula composition is
NaCNO 55%, Na2CO35%, K2CO330%, KOH 5%, Li2CO34%, Na2SO41%.
Embodiment 4
Unlike a kind of environment-friendly type nitridation salt and embodiment 1 for QPQ techniques, by mass, formula composition is
NaCNO 45%, KCNO 10%, Na2CO37%, K2CO335%, Li2CO33%.
Embodiment 5
Unlike a kind of environment-friendly type nitridation salt and embodiment 1 for QPQ techniques, by mass, formula composition is
NaCNO 40%, KCNO 15%, Na2CO37%, K2CO330%, KCl 5%, Li2CO32.5%, Na2SO40.5%.
Comparative example 1
Unlike a kind of environment-friendly type nitridation salt and embodiment 1 for QPQ techniques, by mass, formula composition is
NaCNO 60%, KCNO 10%, Na2CO37%, K2CO315%, KCl 5%, Li2CO32.5%, Na2SO40.5%
Comparative example 2
Unlike a kind of environment-friendly type nitridation salt and embodiment 1 for QPQ techniques, by mass, formula composition is
NaCNO 30%, KCNO 20%, Na2CO37%, K2CO335%, KCl 5%, Li2CO32.5%, Na2SO40.5%.
Comparative example 3
Unlike a kind of environment-friendly type nitridation salt and embodiment 1 for QPQ techniques, by mass, formula composition is
NaCNO 35%, KCNO 10%, Na2CO37%, K2CO340%, KCl 5%, Li2CO32.5%, Na2SO40.5%.
Comparative example 4
Unlike a kind of environment-friendly type nitridation salt and embodiment 1 for QPQ techniques, by mass, formula composition is
NaCNO 45%, KCNO 20%, Na2CO37%, K2CO310%, KCl 15%, Li2CO32.5%, Na2SO40.5%.
Ring prepared by above-described embodiment 1, embodiment 2, embodiment 3 and comparative example 1, comparative example 2, comparative example 3, comparative example 4
It is as shown in table 1 that guarantor's type nitridation salt is formulated the comparison of feature situation：
Environment-friendly type nitridation salt formula feature situation comparison prepared by the different embodiments of table 1
As shown in Table 1, the present invention provides a kind of environment-friendly type nitridation salt for QPQ techniques, as the main component with Zassol,
By mass, including following each component NaCNO 35%-55%, KCNO 0%-20%, Na2CO35%-10%, K2CO3
15%~35%, KCl 0%-15%, KOH 0%-10%, Li2CO30%-5%, Na2SO40%-2%.The nitridation salt with
Zassol is as the main component, using carbonate as fused-salt medium, using sodium sulphate as oxidant, using chloride as energizer, has and oozes
Nitrogen speed is fast, the wide feature of proper temperature range, it is crucial that, this formula nitridation salt not will produce ammonia in fusion process
The characteristics of gas discharges, nontoxic and pollution-free, in melting production process, has dust few, no ammonia release, is a kind of environment-friendly type nitrogen
Salt dissolving.NaCNO KCNO contents are outside the above range, either excessive or too small, and salt bath stability is poor, generation
Nitridation salt cannot stablize use.
The application is as the main component with Zassol and potassium carbonate.No matter how other proportionings arrange in pairs or groups, as long as with cyanic acid
Sodium and potassium carbonate are main component, then within the right of this formula.
It should be noted that the above embodiments are only used to illustrate the technical solution of the present invention., rather than its limitations；Although
Present invention has been described in detail with reference to the aforementioned embodiments, it will be understood by those of ordinary skill in the art that：It is still
Either which part or all technical features can be carried out so that technical scheme described in the above embodiments is modified
Equivalent replacement；And these modifications or replacements, it does not separate the essence of the corresponding technical solution various embodiments of the present invention technical side
The range of case.
Claims (10)
1. a kind of environment-friendly type nitridation salt for QPQ techniques, as the main component with Zassol, it is characterised in that：By mass, it wraps
Include following each component NaCNO 35%-55%, KCNO 0%-20%, Na2CO3 5%-10%, K2CO315% ~ 35%, KCl 0%-
15%, KOH 0%-10%, Li2CO30%-5%, Na2SO4 0%-2%。
2. a kind of environment-friendly type nitridation salt for QPQ techniques as described in claim 1, it is characterised in that：By mass, including
Following each component NaCNO 40%-50%, KCNO 5%-10%, Na2CO35%-10%, K2CO320% ~ 30%, KCl 5%-10%
, KOH 0%-10%, Li2CO32.5%-5%, Na2SO4 0.5%-2%。
3. a kind of environment-friendly type nitridation salt for QPQ techniques as described in claim 1, it is characterised in that：By mass, including
Following each component NaCNO 50%, KCNO 5%, Na2CO35%, K2CO320%, KCl 10%, KOH 5%, Li2CO3 4%
, Na2SO4 1%。
4. a kind of environment-friendly type nitridation salt for QPQ techniques as described in claim 1, it is characterised in that：By mass, including
Following each component NaCNO 45%, KCNO 10%, Na2CO3 7%, K2CO3 35%, Li2CO3 2.5%, Na2SO4
0.5%。
5. a kind of environment-friendly type nitridation salt for QPQ techniques as described in claim 1, it is characterised in that：By mass, including
Following each component NaCNO 35%, KCNO 20%, Na2CO310%, K2CO320%, KCl 5%, KOH 5%, Li2CO3 3%
, Na2SO4 2%。
6. a kind of preparation method of environment-friendly type nitridation salt for QPQ techniques as described in any one of claim 1-5, special
Sign is：Include the following steps：
（1）It prepares：By NaCNO, KCNO, Na2CO3, K2CO3, KCl, KOH, Li2CO3, Na2SO4 It is equal by formula rate mixing
It is even；
（2）Melting：Prepared raw material salt is put into melting in crucible furnace；
（3）Salt cooling is scooped：The nitridation salt molten liquid of smelting completion is scooped out and pours into cooled and solidified in cooler pan；
（4）It packs：Nitridation salt after cooling is packaged into the finished product packing bag of customization, packaging and storage.
7. the preparation method of the environment-friendly type nitridation salt according to claim 6 for QPQ techniques, it is characterised in that：It is described
Step（2）Middle smelting temperature is 600 DEG C ~ 630 DEG C, and the time is 9 ~ 16 hours.
8. a kind of application process of environment-friendly type nitridation salt for QPQ techniques as described in any one of claim 1-5, special
Sign is：Include the following steps：
The additive amount of nitridation salt is calculated by volume and density；
Nitridation salt is added under the conditions of nitrogenizing salt temperature.
9. the application process of the environment-friendly type nitridation salt according to claim 8 for QPQ techniques, it is characterised in that：Step
（1）Middle nitridation salt density is 2100 kilograms per cubic meter.
10. the application process of the environment-friendly type nitridation salt according to claim 8 for QPQ techniques, it is characterised in that：Step
（2）Ranging from 500 DEG C -630 DEG C of middle nitridation salt temperature.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN111763907A (en) * | 2020-08-12 | 2020-10-13 | 北京天仁道和新材料有限公司 | Salt bath nitriding agent for metal workpiece surface treatment and metal workpiece surface treatment method |
| CN112359315A (en) * | 2020-11-10 | 2021-02-12 | 安徽理工大学 | Green low-temperature nitriding agent for titanium alloy surface and method |
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| CN106319438A (en) * | 2015-07-01 | 2017-01-11 | 杭州巨星科技股份有限公司 | Rare earth catalytic permeation QPQ composition and method for manufacturing high-speed cutting tool by QPQ process |
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