CN1059368A - The production method of nitrogen-based controllable atmosphere used for metal thermal treatment - Google Patents

The production method of nitrogen-based controllable atmosphere used for metal thermal treatment Download PDF

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CN1059368A
CN1059368A CN 90107440 CN90107440A CN1059368A CN 1059368 A CN1059368 A CN 1059368A CN 90107440 CN90107440 CN 90107440 CN 90107440 A CN90107440 A CN 90107440A CN 1059368 A CN1059368 A CN 1059368A
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nitrogen
thermal treatment
production method
rare earth
controllable atmosphere
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CN1022577C (en
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杨学仁
刘启英
苏化东
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Shanxi Institute of Coal Chemistry of CAS
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Shanxi Institute of Coal Chemistry of CAS
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Abstract

A kind of production method of nitrogen-based controllable atmosphere used for metal thermal treatment, be that methyl alcohol and industrial general nitrogen feeding are contained in the fixed-bed reactor of methanol decomposition, oxidation dual-function catalyst, oxygen in methanol decomposition generation hydrogen and carbon monoxide and the industrial general nitrogen reacts and removes oxygen, provide methanol decomposition required heat simultaneously, the proportioning that changes methyl alcohol and industrial general nitrogen can be regulated the H of controlled atmosphere easily 2, CO and N 2Content to be satisfying different needs such as machinofacture, metallurgical industry and material industry, this method, and technical process is short, and conversion unit is simple, easy to operate, and temperature of reaction is low, and energy consumption is little.

Description

The production method of nitrogen-based controllable atmosphere used for metal thermal treatment
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 the effect that carburizing and carbon, nitrogen ooze altogether.
CN88103050.3 discloses a kind of production method of nitrogen base reducing atmosphere in the recent period, 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, solved effectively 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, very economical not only, also need huge treating plant, and normal because incomplete combustion makes, and oxygen level in the aerogenesis is higher to limit its widely-used in thermal treatment.
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, under 180-300 ℃, carry out methanol decomposition and oxygen reacts
(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, oxidation dual-function catalyst are the copper zinc chrome series catalysts that contains rare earth, and its compositing range (weight) is: CuO 25-50, ZnO 20-40, 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, residual nitrogen 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, the CO/CO in can the transfer aerogenesis 2Ratio, the air speed of liquid methanol are 0.5-1.5 hour, and 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 suitable for 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 Xunwu, Jiangxi mineral products group of the lanthanides mixed rare-earth oxide for use.
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 γ-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 (weight) is respectively:
A.CuO 2-12
ZnO 1.5-9
Cr 2O 31-7
Rare earth oxide 0.2-3
γ-Al 2O 3100
Total amount/the γ of metal oxide-Al 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
γ-Al 2O 3100
Total amount/the γ of metal oxide-Al 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, vaporization temperature is controlled 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 water 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 -, 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 abundant ground and mixed, send into spraying drying device and carry out drying, nozzle bore 1.8mm, pressure 20kg/cm 2, air themperature is 45 ℃.
Drying gained catalyzer material powder 340 ℃ of following roastings 30 minutes, is played the sheet moulding, get the garden cylindricality catalyzer of φ 4.5mm * 5.5mm, the composition of catalyzer (weight %) is:
CuO 36 ZnO 30 Cr 2O 324.5
K 2O 2.5 rare earth oxides 2.0 graphite 5.0
Annotate: above-mentioned mishmetal is formed (weight):
L?a C?e N?a P?r Y S?m G?d D?y E?r Y?b
33.13?3.08?26.97?11.87?10.94?5.35?3.45?1.09?1.11?1.12
Embodiment 1:
CuO, ZnO, Cr that the above-mentioned coprecipitation method of packing in the high 600mm fixed-bed reactor 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 (when flow is 200ml/) and general nitrogen (0.5m respectively then 3. the time), stablized 1 hour, in 1.5 hours, improve temperature of reaction to 240 ℃ gradually, methyl alcohol and general nitrogen flow increase to gradually 1.5 liters/time and 1.5m 3/ time, stablize again after 1 hour with the ordinary method image data, operation result saw Table 1 in 8 hours:
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(pmm) 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
Change the flow of nitrogen, other same embodiment (1) the results are shown in Table 2.
Table 2
Nitrogen flow M 3/ hour Gas production rate M 3/ hour Liquid receipts ml/hour Aerogenesis is formed (%)
H 2 O2(ppm) N 2 CO CH 4 CO 2
1.5 3.87 132 39.25 39.63 2.4 2.5 39.84 40.64 19.07 19.04 0.406 0.485 1.53 0
2.4 4.75 96 33.26 34.04 3.9 1.3 49.12 49.53 15.55 16.00 0.377 0.412 1.69 0
3.6 6.07 36 26.55 27.17 2.8 5.4 58.89 59.73 12.45 12.79 0.284 0.305 1.82 0
Change other the same embodiment (1) of oxygen level in the nitrogen, the results are shown in Table 3
Table 3
O in the nitrogen 2（％） Gas production rate M 3/ hour Phlegma ml/hour Aerogenesis is formed (%)
H 2 O2(ppm) N 2 CO CH 4 CO 2
0.56 3.85 206 38.60 39.17 4.1 3.6 41.44 41.76 18.95 18.81 0.217 0.252 1.09 0
1.06 3.87 129 39.25 39.63 2.4 2.5 39.84 40.64 19.07 19.04 0.406 0.485 1.53 0
3.22 3.82 24 40.05 41.62 6.1 4.7 38.01 39.53 17.14 18.34 0.319 0.502 4.48 0
Change inlet amount and other same embodiment (1) of temperature of reaction of methyl alcohol, the results are shown in Table 4
Table 4
Alcohol inlet amount liter/hour Temperature of reaction (%) Aerogenesis M 3/ hour Cold liquid ml/hour Aerogenesis is formed (%)
H 2 O2(ppm) N 2 CO CH 4 CO 2
0.8 220 2.76 / 29.66 30.12 4.3 4.5 54.00 54.98 14.33 14.57 0.312 0.328 1.69 0
1.5 245 3.82 132 39.25 39.63 2.4 2.5 39.84 40.64 19.07 19.04 0.406 0.485 1.5 0
2.0 275 4.60 215 44.12 43.24 1.8 1.5 32.83 35.25 21.63 21.06 0.427 0.444 0.9 0
Loading type dual-function catalyst CuO with the infusion method preparation: ZnO: Cr 2O 3: rare earth oxide: γ-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 5
Temperature of reaction 260(℃)
Gas production rate 3.82m 3/ hour
Phlegma 143ml/8 hour
Aerogenesis is formed (%) H 2O 2(pmm) 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 (4)

1, a kind of production method of nitrogen-based controllable atmosphere used for metal thermal treatment 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 copper, zinc, the chromium-based catalysts that contains rare earth, and its compositing range (weight) is:
CuO 25-50
ZnO 20-40
Cr 2O 313-30
Rare earth oxide 1-13.
2, the production method of nitrogen-based controllable atmosphere used for metal thermal treatment as claimed in claim 1 is characterized in that used catalyzer compositing range (weight) is:
CuO 2-12
ZnO 1.5-9
Cr 2O 31-7
Rare earth oxide 0.2-3
γ-Al 2O 3100
Total content/the γ of metal oxide-Al wherein 2O 3=7-25: 100.
3, the production method of nitrogen-based controllable atmosphere used for metal thermal treatment as claimed in claim 1 is characterized in that used catalyzer compositing range (weight) is:
CuO 2-12
ZnO 1.5-8
Cr 2O 31-7
Rare earth oxide 0.2-3
K 2O 0.3-2
γ-Al 2O 3100
Total content/the γ of metal oxide-Al wherein 2O 3=7-25: 100
4, the production method of nitrogen-based controllable atmosphere used for metal thermal treatment as claimed in claim 1 is characterized in that used catalyzer compositing range (weight) is:
CuO 23-48
ZnO 19-39
Cr 2O 313-29
Rare earth oxide 1-12
K 2O 2-6
Graphite 3-8.
CN 90107440 1990-08-31 1990-08-31 Method of preparing nitrogen-based controllable atmosphere used for metal thermal treatment Expired - Fee Related CN1022577C (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
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

Cited By (3)

* Cited by examiner, † Cited by third party
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

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