CN1022577C - Method of preparing nitrogen-based controllable atmosphere used for metal thermal treatment - Google Patents
Method of preparing nitrogen-based controllable atmosphere used for metal thermal treatment Download PDFInfo
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- CN1022577C CN1022577C CN 90107440 CN90107440A CN1022577C CN 1022577 C CN1022577 C CN 1022577C CN 90107440 CN90107440 CN 90107440 CN 90107440 A CN90107440 A CN 90107440A CN 1022577 C CN1022577 C CN 1022577C
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- methanol
- oxygen
- methanol decomposition
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Abstract
The present invention relates to a method for producing a controllable nitrogen base atmosphere used for metal heat treatment. In the method, methanol and general industry nitrogen are led into a fixed bed reactor with a catalyst with the double functions of methanol schizolysis and oxidation, the schizolysis of the methanol is carried out, and hydrogen and carbon monoxide are generated; the hydrogen and the carbon monoxide react with the oxygen of the general industry nitrogen so as to removal the oxygen and simultaneously provide heat needed by the schizolysis of the methanol, and the content of H2, CO and N2 of the controllable atmosphere can be conveniently regulated by changing the proportion of the methanol to the general industry nitrogen so as to satisfy the different needs of machine manufacturing, metallurgical industry and material industry, etc. The method has the advantages of short technological process, simple reaction device, convenient operation, low reaction temperature and less energy consumption.
Description
The invention belongs to the production method of the hydrogeneous gas mixture of nitrogen base, be specifically related to the method that exists the cracking of carapax et plastruw testudinis alcohol catalysis, oxidation to produce hydrogeneous controllable atmosphere of nitrogen at the general nitrogen of industry.
Hydrogeneous and controllable atmosphere of nitrogen carbon monoxide is widely used in machinofacture and metallurgical industry.Be used to handle steel, the steel component of different carbon content, not only can avoid oxidation and decarburization, also can reach carburizing and, the effect of carbonitriding.
CN88103050.3 discloses a kind of production method of nitrogen base reducing atmosphere in the recent period, and this method is to enter fluidized-bed reactor with containing oxygen source nitrogen (normally air) according to a certain ratio with methyl alcohol.In the presence of methyl alcohol burning, catalyst for cracking, the part methanol decomposition generates hydrogen and carbon monoxide, and the oxygen that another part methyl alcohol catalyticcombustion removes in the source nitrogen generates water and carbonic acid gas.This method does not need other nitrogen supply system, effectively solved for the nitrogen problem, but remove oxygen in the source nitrogen with the burning of a large amount of methyl alcohol, generate a large amount of water and carbonic acid gas simultaneously, not only very uneconomical, also need huge treating plant, and often oxygen level is higher to limit its widespread use in thermal treatment owing to incomplete combustion makes in the aerogenesis.
Usually the method that still adopts industrial general nitrogen to be equipped with dissociated methanol gas after purification, deoxidation is produced hydrogeneous controllable atmosphere of nitrogen at present.US4 for example, 249,965 disclose that a kind of methyl alcohol catalytic pyrolysis is produced hydrogen, carbon monoxide is joined nitrogen again or carried the method that the methyl alcohol catalytic pyrolysis is produced hydrogeneous controllable atmosphere of nitrogen with nitrogen.This method energy consumption greatly, also needs other nitrogen supply system or needs in addition the nitrogen treating plant, complex process not only, and also investment is also high.
What the object of the present invention is to provide that a kind of technology is simple, facility investment is few, easy to operate is the method for the hydrogeneous controllable atmosphere of nitrogen of raw material production used for metal thermal treatment with general nitrogen of industry and methyl alcohol.
The production method of nitrogen-based controllable atmosphere used for metal thermal treatment of the present invention may further comprise the steps:
(1) it is 0.5-1.5 hour with air speed
-1Liquid methanol and the industrial general nitrogen that contains 0.1-5% oxygen by methyl alcohol and industrial general nitrogen (in oxygen) mol ratio 0.67: 1-80: 1 feeding is filled with in the fixed-bed reactor of methanol decomposition, oxidation dual-function catalyst, carries out methanol decomposition and oxygen reacts under 180-300 ℃.
(2) the hydrogeneous nitrogen-based gas mixture that obtains of above-mentioned reaction purifies and removes water and carbonic acid gas through cooling,
Described methanol decomposition, deoxidation dual-function catalyst are the copper zinc chrome series catalysts that contains rare earth, and its compositing range (weight %) is: CuO25-50, ZnO20-40, Cr
2O
313-30, rare earth oxide 1-13.
The production method of nitrogen-based controllable atmosphere used for metal thermal treatment of the present invention is the improvement of prior art methanol decomposition method, be to be source nitrogen with the general nitrogen of industry, without purifying directly with methyl alcohol, in the presence of methanol decomposition, oxidation dual-function catalyst, methanol decomposition generates hydrogen and carbon monoxide, and removing oxygen in the industrial general nitrogen, the reaction heat that deoxidation is emitted is required for methanol decomposition.Because industrial general nitrogen oxygen level is moderate, fierce oxidizing reaction can not take place, do not generate a large amount of water and carbonic acid gas, so technical process is short, equipment is simple, easy to operate yet.
The present invention determines the charge ratio of methyl alcohol and industrial general nitrogen according to the composition of required controlled atmosphere.Select the mole proportioning 0.67 of methyl alcohol and industrial general nitrogen (in oxygen): 1-80 for use: 1, correspondingly can obtain O
2＜10ppm, H
2: 1-55%, CO:0-27%, N
2: the controllable atmosphere of nitrogen of 20-99%, and can regulate the composition of controllable atmosphere of nitrogen easily by changing the proportioning of methyl alcohol and industrial general nitrogen.Increase or reduce the proportioning of methyl alcohol and industrial general nitrogen, can improve or reduce the hydrogen in the controllable atmosphere of nitrogen and the content of carbon monoxide.The content range of thermal treatment controlled atmosphere commonly used is: the content of carbon monoxide is 5-20%, is 6.5 so select the ratio range of methyl alcohol and industrial general nitrogen (in oxygen) usually for use: 1-75: 1.
For methyl alcohol can fully be contacted with catalyzer, liquid methanol preferably enters reactor earlier again after vaporization.
Because deoxygenation is thermopositive reaction, so temperature of reaction becomes with the oxygen level in the unstripped gas.When oxygen level was high in the unstripped gas, because heat release automatically, controlled temperature can hang down, and when oxygen level in the unstripped gas was low, controlled temperature should suitably improve, and the temperature range that the present invention allows to use is 180-300 ℃, preferably 200-250 ℃.
Methanol decomposition and nitrogen deoxidation are as easy as rolling off a log two reactions carrying out, and because industrial general nitrogen oxygen level is lower, fierce oxidizing reaction can not take place and cause local superheating, so the present invention selects fixed-bed reactor for use.Fixed-bed reactor are simple in structure, and are easy to operate, can adopt according to the needs of different heat treatment intermittently or the continuous mode operation.The operational condition that the present invention allows is that the purity of methyl alcohol is more than 99%, increases less water in the material benzenemethanol, can regulate the CO/CO in the aerogenesis
2Ratio, the air speed of liquid methanol are 0.5-1.5 hour
-1, the air speed of nitrogen is then decided according to the height of its oxygen level and to the requirement that controlled atmosphere is formed, and generally selects for use 500-5000 hour
-1
Methanol decomposition involved in the present invention, oxidation dual-function catalyst are to implement essential condition of the present invention, the present invention through repetition test, filters out the good copper zinc chrome series catalysts that contains rare earth based on the copper of valence state mutability of the methanol decomposition, the deoxy performance that are fit to technological process of the present invention according to methanol decomposition and the mechanism that purifies deoxidation.Add rare earth and can further improve its thermostability and activity.The present invention selects for use the Xunwu, Jiangxi to produce the group of the lanthanides mixed rare-earth oxide.
Described catalyzer can adopt coprecipitation method to make composite catalyst, also the loaded catalyst that can adopt pickling process to make.Carrier can be silica gel, gac, preferably Y-Al
2O
3
Add an amount of potassium and can improve selectivity of catalyst.
The present invention recommends following several catalyzer, and its compositing range is (with Y-Al
2O
3Weight is 100) be respectively:
A.CuO 2-12
ZnO 1.5-9
Cr
2O
31-7
Rare earth oxide 0.2-3
Total amount/the Y-Al of metal oxide wherein
2O
3=7～25: 100
B.CuO 2-12
ZnO 1.5-8
Cr
2O
31-7
Rare earth oxide 0.2-3
K
2O 0.3-2
Y-Al
2O
3100
Total amount/the Y-Al of metal oxide wherein
2O
3=7-25: 100
C.CuO 23-48
ZnO 19-39
Cr
2O
313-29
Rare earth oxide 1-12
K
2O 2-6
Graphite 3-8
The granularity of catalyzer can be selected according to the size and the processing condition of reactor.The particle of commercial catalysts suitably reduces the granularity of catalyzer generally at 3-6mm, can improve the catalyst surface utilization ratio, thereby improves activity of such catalysts, also can improve life of catalyst.
The present invention is a nitrogenous source with the general nitrogen of industry, in the presence of the dual-function catalyst good in homemade activity, that selectivity is high, inexpensive, does not need other purification directly to produce controllable atmosphere of nitrogen, abundant raw material, and cost is low; Because industrial general nitrogen oxygen level is moderate, reasonable energy utilization not only, oxidizing reaction is milder, equipment and catalyzer is required low, and technology is simple, and is easy to operate, also do not need huge treating plant, invests little.
The present invention can provide different CO, H according to heat treated different needs easily by changing the proportioning of methyl alcohol and industrial general nitrogen
2The controllable atmosphere of nitrogen of content.Not only can satisfy the requirement of metal heat treatmet atmosphere, also can be used as the oxygen-free shielding gas of other production process (as material industry etc.).
Accompanying drawing is a process flow diagram of the present invention.As shown in the figure, liquid methanol is transported to the top of vaporizer (3) by fresh feed pump (1) through surge tank (2), and industrial general nitrogen enters the bottom of vaporizer (3) by self pressure head.Methyl alcohol heats vaporization and enters reactor (4) with industrial general nitrogen after mixing in vaporizer.Vaporizer adopts internal heat type, filler wherein is housed, the device vaporization temperature is at 150-250 ℃, and methyl alcohol is preferably entered by the top of vaporizer, can heat vaporization in the dirty process of liquid, improve vaporization effect, reactor is selected fixed-bed reactor for use, and copper sleeve (5) is equipped with in the centre, is inserted with calrod (6) and temperature regulator (7) in the pipe, heating jacket (8) and controller (9) are equipped with in the reactor outside, and interlayer is filled with dual-function catalyst layer (10).Aerogenesis enters cleaner (12) by the reactor head discharging current and removes unnecessary CO after water condenser (11) condensation removes water and unreacted methanol
2, obtain purpose product gas of the present invention.Cleaner can be arranged in parallel two and be beneficial to switch continuous operation, and the 5A molecular sieve is housed in the cleaner.
Catalyst preparation example:
(1) with purity is 90% 1024kg industry Cu(NO
3)
2Be added in No. 1 still that fills 106kg water under stirring, be mixed with Cu(NO
3)
2Solution.
(2) be that 90.2% 436kg industrial sodium hydroxide is added in No. 2 stills that fill 602kg and is mixed with NaOH solution with purity, be heated to 95 ℃, stir and add above-mentioned Cu(NO down slowly
3)
2Solution, control pH=9 generates Cu(OH)
2Precipitation is filtered, and with 60 ℃ of water washings, removes the Na in the copper hydroxide precipitation
+And NO
+ 3, make Na
+Content is less than 0.15%.
(3) above-mentioned filtration gained Cu(OH)
2Filter cake places still No. 3, adds water 2900kg dilution, is heated to 60, stirs that to add 330kg purity down be that 90.7% ZnO makes the Cu-Zn slip.
(4) be that 90.9% chromic trioxide is added in No. 4 stills that fill the distilled water that is heated to 95 ℃ with 269.5kg purity, be mixed with chromic trioxide solution, under agitation, the Cu-Zn slip in No. 3 stills is added in 2 hours in No. 4 chromic trioxide solution in the still, stirs in half an hour and add 44kgK
2CO
3, and then the lanthanum cerium of stirring adding ore deposit, Xunwu, 20.5kg Jiangxi production respectively is the graphite of mixed rare-earth oxide and 55kg.
(5) with the above-mentioned catalyst slurry for preparing with being pumped into colloidal mill, after fully reseating mixes, send into spray-dryer and carry out drying, nozzle bore 1.8mm, pressure 2.0MPa, air themperature is 450 ℃.
Dry gained catalyzer material powder 340 ℃ of following roastings 30 minutes, is played the sheet moulding, get the cylinder shape catalyst of φ 4.5mm * 5.5mm, catalyzer is formed (weight %) and is:
CuO36ZnO30Cr
2O
324.5K
2O2.5 rare earth oxide 2.0 graphite 5.0
Annotate: above-mentioned mixed rare-earth oxide is formed (weight %):
La Ce Nd Pr Y Sm
33.13 3.08 26.97 11.87 10.94 5.35
Gd Dy Er Yb
3.45 1.09 1.11 1.12
Embodiment 1:
CuO, ZnO, Cr that the above-mentioned coprecipitation method of packing in the fixed-bed reactor of the high 600mm of φ 56mm is produced
2O
3, K
2O, rare earth oxide, 1.5 liters of 2.1kg of graphite catalyst are earlier with 0.2m
3/ hour general nitrogen (oxygen level is 1.06%) exchange system in air, vaporizer and reactor are warming up to 150 ℃ and feed 99.5% liquid methanol (flow is 200ml/ hour) and general nitrogen (0.5m respectively then
3/ hour), stablized 1 hour, in 1.5 hours, improve temperature of reaction to 240 ℃ gradually, methyl alcohol and general nitrogen flow increase to 1.5 liters/hour and 1.5m gradually
3/ hour, stablize again after 1 hour with the ordinary method image data, operation result saw Table 1 in 8 hours:
Change the flow of nitrogen, other same embodiment (1) the results are shown in Table 2.
Change the oxygen level in the nitrogen, other same embodiment (1) the results are shown in Table 3.
Change the inlet amount and the temperature of reaction of methyl alcohol, other same embodiment (1) the results are shown in Table 4.
Loading type dual-function catalyst CuO with the dipping preparation: ZnO: Cr
2O
3: rare earth oxide:
Y-Al
2O
3=6: 4: 2: 1: the 100 same embodiment of other condition (1) in the fixed-bed reactor of embodiment (1) that pack into.Gained the results are shown in Table 5.
Table 1
Gas production rate (normal temperature, normal pressure) 3.87m
3/ hour
Condensing liquid quantity 132ml/8 hour
Water-content in the phlegma＜1%
245 ℃ of temperature of reaction
Aerogenesis is formed (%) H
2O
2(ppm) N
2CO CH
4CO
2
(reaction back) 39.25 2.4 39.74 19.07 0.406 1.53
(purifying the back) 39.83 2.5 40.64 19.04 0.485 0
Table 2
Aerogenesis is formed (%)
Nitrogen flow gas production rate phlegma
m
3/h m
3/h ml/h H
2O
2（ppm） N
2CO CH
4CO
2
1.5 3.87 132 39.25 2.4 39.74 19.07 0.406 1.53
39.63 2.5 40.64 19.04 0.485 0
2.4 4.75 96 33.26 3.9 49.12 15.55 0.377 1.69
34.04 1.3 49.53 16.00 0.412 0
3.6 6.07 36 26.55 2.8 58.89 12.45 0.284 1.82
27.17 5.4 59.73 12.79 0.305 0
Table 3
Aerogenesis is formed (%)
Gas production rate phlegma in the nitrogen
O
2% m
3/h ml/h H
2O
2（ppm） N
2CO CH
4CO
2
0.56 3.85 206 38.60 4.1 41.44 18.95 0.217 1.09
39.17 3.6 41.76 18.81 0.252 0
1.06 3.87 129 39.25 2.4 39.84 19.07 0.406 1.53
39.63 2.5 40.64 19.04 0.485 0
3.22 3.82 24 40.05 6.1 38.01 17.14 0.319 4.48
41.62 4.7 39.53 18.34 0.502 0
Table 4
Methyl alcohol reaction gas production rate phlegma aerogenesis is formed (%)
Inlet amount temperature m
3/ h ml/h
l/h ℃ H
2O
2（ppm） N
2CO CH
4CO
2
0.8 220 2.76 / 29.66 4.3 54.00 14.33 0.312 1.69
30.12 4.5 54.98 14.57 0.328 0
1.5 245 3.82 132 39.25 2.4 39.84 19.07 0.406 1.53
39.63 2.5 40.64 19.04 0.485 0
2.0 275 4.60 215 44.12 1.8 32.83 21.63 0.427 0.99
43.24 1.5 35.25 21.06 0.444 0
Table 5
260 ℃ of temperature of reaction
Gas production rate 3.82m
3/ hour
Phlegma 143ml/8 hour
Aerogenesis is formed (%) H
2O
2(ppm) N
2CO CH
4CO
2
(reaction back) 39.01 3.6 39.84 18.54 0.545 2.06
(purifying the back) 39.83 2.8 40.56 19.04 0.562 0
Claims (3)
1, a kind of production method of nitrogen-based controllable atmosphere used for metal thermal treatment is characterized in that may further comprise the steps:
(1) it is 0.5-1.5 hour with air speed
-1Liquid methanol and the industrial general nitrogen that contains 0.1-5% oxygen by methyl alcohol and industrial general nitrogen (in oxygen) mol ratio 0.67: 1-80: 1 feeding is filled with in the fixed-bed reactor of methanol decomposition, oxidation dual-function catalyst, under 180-300 ℃, carry out methanol decomposition and oxidizing reaction
(2) the hydrogeneous nitrogen-based gas mixture cooling of above-mentioned reaction gained purifies and removes water and carbonic acid gas,
Described methanol decomposition, oxidation dual-function catalyst are the composite catalysts of the copper that contains rare earth, zinc, chromium system, and its composition (weight percentage) is as follows:
CuO 25-50%
ZnO 20-40%
Cr
2O
313-30%
Rare earth oxide 1-13%
2, a kind of production method of nitrogen-based controllable atmosphere used for metal thermal treatment is characterized in that may further comprise the steps:
(1) it is 0.5-1.5 hour with air speed
-1Liquid methanol and the industrial general nitrogen that contains 0.1-5% oxygen by methyl alcohol and industrial general nitrogen (in oxygen) mol ratio 0.67: 1-80: 1 feeding is filled with in the fixed-bed reactor of methanol decomposition, oxidation dual-function catalyst, under 180-300 ℃, carry out methanol decomposition and oxidizing reaction
(2) the hydrogeneous nitrogen-based gas mixture cooling of above-mentioned reaction gained purifies and removes water and carbonic acid gas,
Described methanol decomposition, oxidation dual-function catalyst composed as follows (with Y-Al
2O
3Weight be 100):
CuO 2-12%
ZnO 1.5-9%
Cr
2O
31-7%
Rare earth oxide 0.2-3%
Total amount/the Y-Al of metal oxide wherein
2O
3=7～25: 100.
3, the production method of nitrogen-based controllable atmosphere used for metal thermal treatment as claimed in claim 2 is characterized in that described catalyzer is composed as follows (with Y-Al
2O
3Weight is 100):
CuO 2-12%
ZnO 1.5-8%
Cr
2O
31-7%
Rare earth oxide 0.2-3%
K
2O 0.3-3%
Total amount/the Y-Al of metal oxide wherein
2O
3=7～25: 100
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90107440 CN1022577C (en) | 1990-08-31 | 1990-08-31 | Method of preparing nitrogen-based controllable atmosphere used for metal thermal treatment |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90107440 CN1022577C (en) | 1990-08-31 | 1990-08-31 | Method of preparing nitrogen-based controllable atmosphere used for metal thermal treatment |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1059368A CN1059368A (en) | 1992-03-11 |
| CN1022577C true CN1022577C (en) | 1993-10-27 |
Family
ID=4880551
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90107440 Expired - Fee Related CN1022577C (en) | 1990-08-31 | 1990-08-31 | Method of preparing nitrogen-based controllable atmosphere used for metal thermal treatment |
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|---|---|
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1038667C (en) * | 1993-07-13 | 1998-06-10 | 中国科学院山西煤炭化学研究所 | Method and apparatus for preparing nitrogen atmosphere by barrier separation for metallic heat treatment |
| CN1086598C (en) * | 1999-07-21 | 2002-06-26 | 中国科学院山西煤炭化学研究所 | Method for separating and removing high conentration nitrogen dioxide and equipment thereof |
| CN114751386A (en) * | 2022-05-26 | 2022-07-15 | 江苏中科聚元氢能源科技有限公司 | General nitrogen deoxidization purification method and device based on methanol cracking reaction |
-
1990
- 1990-08-31 CN CN 90107440 patent/CN1022577C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
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