CN1014973B - Technique and equipment for producing reduction atmosphere with nitrogen - Google Patents
Technique and equipment for producing reduction atmosphere with nitrogenInfo
- Publication number
- CN1014973B CN1014973B CN 88103050 CN88103050A CN1014973B CN 1014973 B CN1014973 B CN 1014973B CN 88103050 CN88103050 CN 88103050 CN 88103050 A CN88103050 A CN 88103050A CN 1014973 B CN1014973 B CN 1014973B
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- China
- Prior art keywords
- methyl alcohol
- nitrogen
- reactor
- silica gel
- fluidized
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a production method for nitrogen group reducing atmosphere containing H2 and CO. According to the molar ratio of 0.67 to 3:1, methanol and air (measured by oxygen) are introduced into a fluidized bed reactor with a wearproof catalyst with the dual functions of combustion resistance and cracking resistance to simultaneously carry out combustion and cracking reaction at a normal pressure of 250 to 700 DEG C; gas mixtures obtained in reaction is cooled and purified. The technology of the present invention has the advantages of low reaction temperature, little energy consumption and no need of additional nitrogen supply systems; through changing the air and methanol proportion, the H2, CO and N2 contents can be conveniently regulated to meet different requirements in the aspects of mechanical manufacture, metallurgical industries, controlled atmosphere storage, etc.
Description
The invention belongs to the production method of nitrogen base reducing atmosphere, be specifically related to the production method and the equipment of the nitrogen base reducing atmosphere of hydrogeneous, carbon monoxide.
Nitrogen base reducing atmosphere hydrogeneous, carbon monoxide not only is widely used in machinofacture and metallurgical industry, but also can be used for grain and oil, medicinal material, metal and chemical preparations,, the anaerobic storage of rare cultural relics and archives material etc., the production technique of therefore studying this atmosphere is significant.
Early stage as US3,519,257(1970) disclose that the production of hydrocarbon fuel incomplete combustion is hydrogeneous, the method for the nitrogen base reducing atmosphere of carbon monoxide.This method temperature of reaction is up to 900-1000 ℃, and nitrogen supply system that in process of production often need be other replenishes nitrogenous source, the strict anaerobic of also wayward product.
Recent as US4,249,965(1981) adopt the catalyst for methanol cracking process.The methyl alcohol catalytic pyrolysis is produced hydrogen, carbon monoxide, joins nitrogen again or carry the methyl alcohol catalytic pyrolysis with nitrogen to obtain nitrogen base reducing atmosphere hydrogeneous, carbon monoxide, and methanol decomposition is a strong endothermic reaction, and energy consumption is big, and also needs other nitrogen supply system.
Nitrogen base reducing atmosphere production method and the corresponding apparatus thereof of the object of the present invention is to provide that a kind of temperature of reaction is low, energy consumption is little, need not other nitrogen supply system, product gas being formed adjustable hydrogeneous and carbon monoxide.
The production method of the nitrogen base reducing atmosphere of hydrogeneous and carbon monoxide provided by the invention may further comprise the steps:
1) methyl alcohol and source nitrogen feed the reactor that is filled with catalyzer according to a certain ratio and carry out catalyzed reaction,
2) reaction gained nitrogen-based gas mixture hydrogeneous and carbon monoxide cools off, purifies,
It is characterized in that described source nitrogen is the source nitrogen that contains 5-30% oxygen, methyl alcohol is 0.67 with the proportioning that contains oxygen source nitrogen (in oxygen): 1-3: 1, and described catalyzer is methyl alcohol burning, cracking dual-function catalyst, reactor is selected fluidized-bed reactor for use.
In the presence of methyl alcohol burning, cracking dual-function catalyst, methanol decomposition and combustion reactions are carried out in same reactor.The consumption of methyl alcohol catalyticcombustion contains the oxygen in the oxygen source nitrogen, and residual nitrogen is emitted reaction heat simultaneously methanol decomposition institute energy requirement is provided, and methanol decomposition generates hydrogen and carbon monoxide.Select the source nitrogen of different oxygen for use or change the relative content that methyl alcohol and the proportioning that contains the oxygen source nitrogen can be regulated carbon monoxide, hydrogen and nitrogen in the product gas.
Source nitrogen involved in the present invention is meant and is the required unstripped gas that contains nitrogen of production purpose atmosphere.The oxygen source nitrogen that contains of the present invention is preferably selected normal air for use, both conveniently is easy to get, cost is also low, also can select rich nitrogen or oxygen-rich air for use.Oxygen-rich air is suitable for producing high hydrogen carbon monoxide content atmosphere, and nitrogen-rich air is suitable for producing low hydrogen low CO content atmosphere.
Methyl alcohol of the present invention is meant methyl alcohol and the mole ratio that contains oxygen in the oxygen source nitrogen with the proportioning that contains the oxygen source nitrogen, and its big I is made of selected required atmosphere.Need H
2When high, should select higher proportioning with CO content, but proportioning increases, the ratio of methanol decomposition increases thereupon, and temperature of reaction descends; Otherwise then temperature rises because methyl alcohol burning ratio increases.So the variation range of proportioning should be adapted to the temperature range that is suitable for of catalyst system therefor.The permission use temperature scope of the catalyzer of the present invention's development is 250-700 ℃, and preferably 400-600 ℃, therefore methyl alcohol of the present invention was selected for use 0.67: 1 to 3: 1 with the proportioning that contains the oxygen source nitrogen, contained the CO of 0-20% in the corresponding product gas approximately, the H of 0-40%
2(dry gas) can adapt to different needs.
The present invention generally selects the industrial refined methanol more than 99% for use, can add an amount of water when needing control reaction temperature or avoiding tying charcoal.For preventing to tie charcoal, also should avoid using the thick methyl alcohol contain high-boiling-point impurity (as higher alcohols) or reclaim methyl alcohol without distillatory.Interpolation adequate amount of ethanol or light hydrocarbon fuel can improve the methane content in the product gas, are suitable for doing high carbon potential thermal treatment protection gas and use.
The burning of the used methyl alcohol of the present invention, cracking dual-function catalyst can be the combustioncatalysts used always and the mechanical mixture or the compound prescription catalyzer of methanol cracking catalyst, and for example noble metal combustion catalyst and copper base or zinc chrome are the mechanical mixture or the compound prescription catalyzer of these components on identical carrier of methanol cracking catalyst.
Noble metal support type dual-function catalyst or compound base metal oxide loading type dual-function catalyst that dual-function catalyst of the present invention preferably selects for use the present invention to develop.
Described noble metal carrier catalyst, preferably palladium is that precious metal is stated from the catalyzer on silica gel, aluminum oxide or its complex carrier.Precious metal component palladium preferably wherein, carrier preferably is coated with Al
2O
3Silica gel, the compositing range of reasonable catalyzer is:
Pd: silica gel (is coated with Al
2O
3)=0.1-5.0: 100(weight) preferably select Pd for use: silica gel (is coated with 15.6%Al
2O
3)=0.3-1.0: 100(weight)
This catalyzer adopts general infusion method preparation.
Described compound base metal oxide loading type dual-function catalyst is to be stated from silica gel, Al
2O
3Or TiO
2Etc. the O composite metallic oxide catalyst that includes I B family metal oxide, VI B family metal oxide and VIII family base metal oxide at least on the attrition-resistant support.Wherein I B family metal is preferably selected copper or silver for use, and VI B family metal is preferably selected chromium for use, and VIII family base metal is preferably selected nickel or cobalt for use, and carrier is preferably selected microsphere silica gel for use.
The compositing range of the catalyzer that recommendation is selected for use (weight) is:
Cr
2O
32-10
CuO 1-6
NiO 1-6
Microsphere silica gel 100
The total amount of metal oxide: silica gel=6-20 wherein: 100(weight)
In order to improve the combustionproperty of this catalyzer, preferably add an amount of VII B family metal oxide, preferably manganese oxide.The compositing range (weight) of the catalyzer that the present invention recommends is:
Cr
2O
32-10
CuO 1-6
NiO 1-6
MnO 1-5
Microsphere silica gel 100
The total amount of metal oxide: silica gel=6-20 wherein: 100(weight)
This Preparation of catalysts method belongs to prior art, can select infusion method for use.
The granularity of above-mentioned catalyzer and shape are according to reactor size, and catalyst fluidization characteristic such as particle incipient fluidizing velocity and carrying velocity etc. are selected, can select 30-80 purpose microballoon or amorphous pellets catalyzer usually for use.
Realize the equipment of above-mentioned technology, comprise material-transporting system, cooling, the purification system of reactor and reaction gained gaseous mixture is characterized in that described reactor is a fluidized-bed reactor
Fig. 1 is a process flow diagram.
The present invention by reference to the accompanying drawings production technology and equipments of the nitrogen base reducing atmosphere of 1 pair of hydrogeneous, carbon monoxide is described further.
The material-transporting system that the present invention relates to can be selected arbitrarily suitable existing conveying equipment, and the material-transporting system that the present invention selects mainly comprises the air blast (3) of carrying methyl alcohol storage tank (1) that methyl alcohol uses and feed pump (2), carrying air to use.
Since methyl alcohol with contain the oxygen source nitrogen and can form explosive mixture (methyl alcohol explosion limit concentration is 6.72-36.5%), set off an explosion easily. The present invention adopts fluidized-bed reactor, not only can avoid explosion danger, and because the abundant disturbance of gas-solid two-phase, good heat-transfer, reaction bed temperature are even, can avoid hot-spot to cause catalysqt deactivation, thereby improve the efficient of reactor.
For large-scale fluidized bed reactor, methyl alcohol directly adds fluidized-bed layer, and internals such as gas distribution grid can also be set, and radiating piece etc. can also arrange expanding reach on fluidized-bed reactor top as required to improve distribution of gas and heat transfer property in the fluid bed.
For the small-sized fluidized bed reactor, can arrange one in fluidized-bed reactor bottom and fill Packed premixer, after being mixed, methyl alcohol and air pass into again fluidized-bed reactor.
For preventing causing not exclusively that because of the fluidized-bed reactor internal reaction residual methanol and remaining oxygen are too high, one joint can be set in the fluidized-bed reactor exit with the fixed-bed conversion device of premixer, the fixed bed inner catalyst can be identical with the fluid bed reactor catalysis agent, also can be different.
The volume velocity of fluidized-bed reactor should be according to the size of reactor, the character of selected catalyst, and the oxygen content of source of the gas, methyl alcohol is selected with the proportioning that contains the oxygen source nitrogen and gas production etc., when the present invention selects 3000-5000-1。
Reactor among Fig. 1 is a kind of reactor schematic diagram that the present invention selects, and comprises the fixed-bed conversion device (6) of fluidized-bed reactor (4) and band premixer (5).
Cooling of the present invention, cleaning system remove unreacted methyl alcohol in order to cooling reaction gained gas, can further remove as required the CO that reaction generates2And water, can select any prior art for example water condenser or water spray column be used for cooling and methanol removal, select active carbon, potash or molecular sieve to remove CO2, select molecular sieve, silica gel or alumina removal water. Cooling of the present invention, cleaning system comprise water-cooling tower (7), compressor (8), water condenser (9), gas-liquid separator (10), CO as shown in Figure 12Remove device (11) and dry cleaner (12). Cool off and remove through water cooling tower (7) from the reaction gas mixtures of fixed-bed conversion device (6) and enter CO unreacted methyl alcohol is isolated the water of condensation by compressor (8) compression, water condenser (9) condensation, gas-liquid separator (10) after2Remove device (11) and remove part CO2, enter again dry cleaner (12) and further remove remaining CO2And water. In order to make complete machine energy continuous operation, cleaning system is preferably by two or more switchable CO2Removing device and drier forms.
The present invention is with the methyl alcohol of certain proportioning and contains the oxygen source nitrogen, in burning, under the effect of cracking bifunctional catalyst, methanol decomposition and methyl alcohol combustion reaction are carried out in same reactor, and the methanol oxidation burning consumes the oxygen that contains in the oxygen source nitrogen, residual nitrogen, emit simultaneously reaction heat and provide energy for methanol decomposition, therefore, compared with prior art, reaction temperature of the present invention is low, except starting, heat can be self-supporting, and energy is fully used, and does not need other nitrogen supply system.
The present invention can regulate the aerogenesis composition by changing methyl alcohol and the proportioning that contains the oxygen source nitrogen easily, and different CO, H are provided2Content contains or does not contain CO2With the nitrogen base reducing atmosphere of water, to satisfy the different needs of the aspects such as machine-building and metallurgical industry and controlled atmospher storage.
Embodiment 1:
The granularity of packing in the stainless steel fluidized-bed reactor of-high 300mm of Φ 100mm is the 30-80 order, Cr
2O
3: CuO: NiO: MnO: silica gel=4: 2: 2: 2: dual-function catalyst 300ml 100(weight).The fixed-bed conversion device of one section high 100mm of Φ 100mm is arranged at reactor top, interior dress 10-20 order NiO: K
2CO
3: Al
2O
3=15: 2: catalyzer 300ml 100(weight), with 1 meter
3The air in/time makes the fluid catalyst fluidisation, and make catalyzer temperature-elevating to 250 ℃ with heating jacket, in the Packed premixed device in fluidized-bed bottom, send into industrial refined methanol (purity is more than 99%), the control flow velocity 460 milliliters/time, reaction takes place immediately, and reaches stable state in one hour.Service data mean value saw Table 1 in eight hours.
Embodiment 2:
With Cr
2O
3: CuO: NiO: silica gel=4: 3: 3: 100 30-80 order catalyzer is packed in the fluidized-bed as embodiment 1, and all the other the results are shown in Table 2 with embodiment 1.
Embodiment 3:
Fluid catalyst adopts 0.5Pd: 100SiO
2(contain Al
2O
315.6%) (8801), 0.5Pt: 100SiO
2(contain Al
2O
315.6%) (8802), and 0.5Pd: 100SiO
2(do not contain Al
2O
3) (8804).All the other are with embodiment 1.The results are shown in Table 3.
Embodiment 4:
Change the methanol feeding amount, all the other are with embodiment 1.Fluid bed section reaction result such as table 4.
Embodiment 5:
In methyl alcohol, mix 10%(weight) dehydrated alcohol or non-leaded gasoline, all the other are with embodiment 1.The results are shown in Table 5.
Table 1:
1.57 meters of gas production rate (normal temperature and pressure)
3/ time
153 milliliters of condensation water quantities/time
Methanol content in the water of condensation＜1%
Temperature of reaction ℃ aerogenesis is formed %
CO
2H
2CO CH
4O
2N
2
Fluidized-bed 443 6.2 24.7 17.6 0.004 0 51.4
Fixed bed 288 6.8 25.0 16.9 0.106 0 51.2
Table 2:
1.46 meters of gas production rate (normal temperature and pressure)
3/ time
208 milliliters of condensation water quantities/time
Methanol content 7.9% in the water of condensation
469 ℃ of fluidized-bed reaction temperature
CO
2H
2CO CH
4O
2N
2
The fluidized-bed aerogenesis is formed % 6.8 16.7 14.7 0.012 0 61.2
Table 3
Catalyzer 8,801 8,802 8804
Fluidized-bed temperature ℃ 453 449 438
Gas production rate rice
3/ time 1.65 1.63 1.68
Aerogenesis is formed the %(fluidized-bed)
CO
24.5 8.8 5.7
H
217.7 25.1 23.4
CO 18.3 12.6 18.0
CH
40.38 1.14 0.03
O
20 0 0
N
259.1 52.3 52.9
Condensation water quantity milliliter/time 160 135 133
Methanol content % 2.14 0.97 1.51 in the water of condensation
Table 4
Methanol feeding speed (milliliter/time) 300 325 350 375 420 460
Fluidized-bed reaction temperature ℃ 621 584 595 595 514 443
Gas production rate (rice
3/ time)--1.45 1.55 1.52 1.57
Condensation water quantity (milliliter/time)--171 169 158 153
Produce CO
211.06 10.06 8.9 9.4 9.2 6.2
Gas H
23.84 5.16 6.0 8.7 21.8 24.7
Group CO 5.03 6.04 8.0 8.4 12.0 17.6
Become CH
400 0.013 0.012 0.057 0.094
（%） O
20.51 0.16 0.29 0.11 0 0
N
279.0 78.0 76.8 73.4 56.9 51.4
Table 5
Fuel methanol+10% dehydrated alcohol methyl alcohol+10% non-leaded gasoline
Fluidized-bed temperature ℃ 487 490
Aerogenesis is formed the %(fluidized-bed)
CO
26.7 7.1
H
219.0 22.4
CO 15.5 15.5
CH
40.80 0.062
O
20 0
N
258.0 54.9
Claims (7)
1, a kind of production method of nitrogen base reducing atmosphere of hydrogeneous and carbon monoxide may further comprise the steps:
(1) methyl alcohol and source nitrogen feed the reactor that is filled with catalyzer according to a certain ratio and carry out catalyzed reaction,
(2) reaction gained nitrogen-based gas mixture hydrogeneous and carbon monoxide cools off, purifies,
It is characterized in that the described source nitrogen that contains is the source nitrogen that contains 5-30% oxygen, methyl alcohol is the industrial refined methanol more than 99%, methyl alcohol is 0.67 with the proportioning that contains oxygen source nitrogen (in oxygen): 1-3: 1, reaction conditions is normal pressure 250-700 ℃, described catalyzer is methyl alcohol burning, cracking dual-function catalyst, and reactor is selected fluidized-bed reactor for use.
2, the method for claim 1 is characterized in that described methyl alcohol burning, cracking dual-function catalyst are the precious metal dual-function catalysts that is stated from silica gel, aluminum oxide or its complex carrier.
3, method as claimed in claim 2 is characterized in that described precious metal dual-function catalyst is to be stated to be coated with Al
2O
3Silica gel on palladium catalyst, its compositing range is:
Pd: silica gel (Al
2O
3)=0.1-5.0: 100(weight).
4, the method for claim 1 is characterized in that described methyl alcohol burning, cracking dual-function catalyst are the O composite metallic oxide catalysts that contains I B family metal oxide, VI B family metal oxide and VIII family base metal oxide that is stated from the attrition-resistant support such as silica gel, aluminum oxide or titanium dioxide.
The total amount of metal oxide: silica gel=6-20 wherein: 100(weight).
5, method as claimed in claim 4 is characterized in that the compositing range (weight) of described compound base metal oxide catalyzer is:
Cr
2O
32-10
CuO 1-6
NiO 1-6
MnO 1-5
Microsphere silica gel 100
The total amount of metal oxide: silica gel=6-20 wherein: 100(weight).
6, realize the equipment of the described method of claim 1, comprise cooling, the purification system of material-transporting system, reactor and reaction gained gaseous mixture, it is characterized in that described reactor is a fluidized-bed reactor 4.
7, equipment as claimed in claim 6 is characterized in that the fixed-bed conversion device 6 that described reactor comprises fluidized-bed reactor 4 and is positioned at exit, fluidized-bed reactor 4 top.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88103050 CN1014973B (en) | 1988-05-19 | 1988-05-19 | Technique and equipment for producing reduction atmosphere with nitrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88103050 CN1014973B (en) | 1988-05-19 | 1988-05-19 | Technique and equipment for producing reduction atmosphere with nitrogen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1037688A CN1037688A (en) | 1989-12-06 |
| CN1014973B true CN1014973B (en) | 1991-12-04 |
Family
ID=4832419
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88103050 Expired CN1014973B (en) | 1988-05-19 | 1988-05-19 | Technique and equipment for producing reduction atmosphere with nitrogen |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1014973B (en) |
Families Citing this family (1)
| 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 |
-
1988
- 1988-05-19 CN CN 88103050 patent/CN1014973B/en not_active Expired
Also Published As
| Publication number | Publication date |
|---|---|
| CN1037688A (en) | 1989-12-06 |
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