CN1095440C - Hydrogen-making process of dry-gas selective catalyst oxidation for oil refinery - Google Patents
Hydrogen-making process of dry-gas selective catalyst oxidation for oil refinery Download PDFInfo
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- CN1095440C CN1095440C CN98113758A CN98113758A CN1095440C CN 1095440 C CN1095440 C CN 1095440C CN 98113758 A CN98113758 A CN 98113758A CN 98113758 A CN98113758 A CN 98113758A CN 1095440 C CN1095440 C CN 1095440C
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Abstract
The present invention relates to a technology method for producing hydrogen by the selecton of the catalysis and the oxidation of refinery dry gas. Refinery dry gas is selectively oxidized so as to form CO and H2 under the action of multicomponent Ni-based catalysts, wherein the CO can be converted into the H2 by using water vapour, and finally, a large number of H2 resources can be obtained by separation and purification. The technology method is carried out in a fixed bed reactor or a fluidized-bed reactor at reaction temperature of 450 to 950 DEG C and normal atmosphere of-1MPa, C/O2 is in a scope ranging from 2 to 1.9, and the air speed of a gas reaction is in a 0.8 to 3.0x10<5>h<-1>. Substances of C2 H4, C2 H6 and C3 in the dry gas are completely converted, the conversion rate of CH4 can reach 96.8%, the selectivity of the CO is 90.8%, and the selectivity of the H2 is 98.5%. The method has the advantages of high air speed, low energy consumption, economy, etc., and is suitable for producing hydrogen by using the refinery dry gas as raw materials.
Description
The present invention relates to a kind of technological process of on polycomponent Ni base or other effective noble metal catalyst, producing hydrogen by dry-gas selective catalyst oxidation for oil refinery.
Oil refinery dry gas comprises catalytic cracked dry gas, and coking dry gas and all contain the discharging gas of low-carbon (LC) hydro carbons, and it is the big tail gas of combining of petroleum chemical enterprise's discharging, and a large amount of CH is wherein arranged
4, C
2H
6, C
2H
4, C
3H
6Deng useful matter.Owing to form complexity in the gas, be difficult to separate and utilize, oil refinery dry gas is used mainly as combustion gas at present, and utility value is low.Along with the development of oil deep processing, need many hydrogenation processes in order to improve oil quality and value-added content of product; By 2000, China will introduce up to 5,000 ten thousand tons of high sulfur content crude oil in addition, be the protection environment, and hydrogenating desulfurization is imperative, H
2The source has been " bottleneck " of restriction petroleum chemical enterprise development.Traditional steam reformation hydrogen production facility investment is big, takies raw materials such as lighter hydrocarbons again, hydrogen manufacturing cost height.If with the oil refinery dry gas is raw material, adopt the gating catalytic oxidation legal system to get hydrogen: 1. the utility value of oil refinery dry gas is improved greatly; 2. the energy consumption that has overcome traditional steam reformation hydrogen production is big, the low and big shortcoming of facility investment of air speed.It is low that this reaction process has energy consumption, CO, H
2The characteristics that selectivity is high, and reaction can be operated under low pressure, big air speed condition.
The object of the invention provide a kind of economy, be applicable to suitability for industrialized production, be the method that raw material is produced hydrogen with the oil refinery dry gas.
The present invention adopts through the multi-component Ni-based catalyst behind the auxiliary agent modulation (Chinese patent application number 96115030.0) or other effective noble metal catalyst, in fixed bed or fluidized-bed reactor, under big air speed condition, is H with the oil refinery dry gas selective oxidation
2And CO, after the selective oxidation in the catalysis drying gas CO then can adopt industrial sophisticated already water vapor conversion to convert H to
2, the H in the last dry gas
2Can obtain a large amount of H through transformation fractionation by adsorption or membrane sepn purification
2Gas, its technical process as shown in Figure 1.
Specifically, the processing method that is used for oil refinery dry gas selective oxidation hydrogen manufacturing of the present invention comprises:
A. dry gas (1) and oxygen (2) in mixing tank, carry out catalytic selective oxidation (3) in proportion;
B. CO feeds water vapor (5) and carries out synthetic gas transformationreation (6) in the catalysis drying gas after selective oxidation in mixing tank (4);
C. the H in the last dry gas
2Isolate hydrogen (8) and tail gas (9) through transformation absorption or membrane sepn purification (7);
The reaction conditions of step a is: temperature of reaction is 450～950 ℃; Gas space velocity is 0.8～3.0 * 105h
-1Reaction pressure is normal pressure～1MPa; C/O in the reactant gases
2=2～1.9.
In the method for the invention, can adopt fixed bed or fluidized-bed among the step a is CO and H with the oil refinery dry gas catalytic selective oxidation
2Multi-component Ni-based catalyst (the branch art that the composition of concrete catalyzer and preparation are provided with reference to Chinese patent application numbers No. 96115030.0) or other effective noble metal catalyst are adopted in this catalytic selective oxidation reaction simultaneously.
Oil refinery dry gas in the present invention is meant that catalytic cracked dry gas, coking dry gas and all contain the discharging gas of low-carbon (LC) hydro carbons.For example, Fushun Petrochemical Company is refined oil the catalysis of two factories in gas, wherein CH
4: 30.6%, CO
2: 1.7%, C
2H
4: 21.3%, C
2H
6: 18.3%, H
2: 5.3%, CO:0.5%, N
2: 22.4%,
After handling with selective oxidation method of the present invention.CH
4Transformation efficiency can reach more than 90%, C
2H
4, C
2H
6, C
3H
6, C
3H
6Substantially fully transform H in the product
2, the selectivity of CO is up to 90%.The reaction after product is formed; Hydrogen accounts for 40～50%, and CO accounts for 30～40%, H
2+ CO accounts for 80%, all the other N
2+ CO
2+ CH
4Sum is less than 20%.Wherein CO then can adopt the water vapor conversion to convert H to
2, the H in the last dry gas
2Can reach about 80%, can obtain heavy greatly H through transformation fractionation by adsorption or membrane sepn purification
2Gas.
The technology of the present invention details is by the detailed description in addition of following example:
Embodiment 1
Take by weighing multi-component Ni-based catalyst (by Chinese patent application numbers 96115030.0) 0.030 gram, be loaded on by silica glass and fire in the fixed-bed reactor that form, tube inner diameter is 4mm, and temperature-measuring heat couple is placed on the middle part (other implement to adopt with sampling device and catalyzer) of catalyst bed.
This reactor feed gas is respectively through N
2The single-component gas of dilution: CH
4(25%), C
2H
4(15%), C
2H
6(15%), C
3H
6(15%), C
3H
8(10%), oxygenant is a pure oxygen.Each gas is all allocated suitable oxygen into according to chemical reaction metering separately, as C
2H
4/ O
2=1: 1.Temperature of reaction is controlled at 700 ℃, and under the normal pressure, total air speed is 3.0 * 10
5h
-1, reaction result is listed in table l.
The reaction result of five kinds of reactant gases gating catalytic oxidations of table 1
Unstripped gas transformation efficiency (%) selectivity (%) H
2/ CO
CO CO
2 H
2
CH
4 84.2 84.7 15.3 98.9 2.33
C
2H
4 100 92.1 7.9 100 1.17
C
2H
6 97.4 89.0 11.0 100 1.71
C
3H
6 100 88.6 11.4 100 1.27
C
3H
6 100 86.5 13.5 100 1.73
This reactor feed gas is CH
4, oxygenant is pure oxygen and air, wherein CH
4/ O
2=2.0.Temperature of reaction is 700 ℃, and air speed is 3.0 * 10
5h
-1, reaction result and tail gas composition see Table 2.
Table 2 air and pure oxygen be during as oxygenant, CH
4The reaction result of gating catalytic oxidation and tail gas are formed
Oxygenant transformation efficiency (%) selectivity (%) tail gas is formed (%) CH
4CO CO
2H
2H
2CO N
2O
2CH
4CO
2
Air 88.5 88.1 11.9 99.5 37.3 16.5 41.6 0 2.4 2.2
Pure oxygen 96.2 92.7 7.3 100 66.2 30.2 00 1.21 2.42
Embodiment 3
This reactor feed gas is that Fushun Petrochemical Company is refined oil the catalysis drying gas (CH wherein of two factories
4: 30.6%, CO
2: 1.7%, C
2H
4: 21.3%, C
2H
6: 18.3%, H
2: 5.3%, N
2: 22.4%, CO:0.5%,
%), oxygenant is pure oxygen, wherein dry gas/O
2Mol ratio is 1.78.Reaction velocity is 1.5～3.0 * 10
5h
-1, temperature of reaction is 600 ℃, reaction result sees Table 3.
Under the different air speeds of table 3, the reaction result of catalytic cracked dry gas gating catalytic oxidation
Air speed transforms thing (%) selectivity (%) (* 10
-5h
-1) CH
4C
2H
8C
2H
4CO CO
2H
23.0 96.8 100 100 90.8 9.2 98.52.0,91.8 100 100 87.9 12.1 99.81.5 83.3 100 100 82.4 17.6 100
Embodiment 4
The catalytic cracked dry gas that this reactor feed gas and embodiment 3 are identical, oxygenant is pure oxygen, wherein dry gas/O
2Mol ratio is 1.78.Reaction velocity is 3.0 * 10
5h
-1, temperature of reaction is 450～650 ℃, reaction result is listed in table 4.
Table 4 differential responses temperature to the catalytic cracked dry gas gating catalytic oxidation influence temperature of reaction transformation efficiency (%) selectivity (%) (℃) CH
4CO CO
2H
2450 93.4 88.0 12.0 99.8 500 94.8 89.1 10.9 99.3 550 96.0 90.3 9.7 98.7 600 96.8 90.8 9.2 98.5 650 97.3 91.7 8.3 98.0
* C
2H
4, C
2H
6, C
3H
6, C
3H
8Transformation efficiency is 100%
Embodiment 5
The catalytic cracked dry gas that this reactor feed gas and embodiment 3 are identical, oxygenant is a pure oxygen, dry gas/O
2Mol ratio is 1.78.Under the differential responses condition, the tail gas of catalytic cracked dry gas gating catalytic oxidation hydrogen manufacturing composition is listed in table 5.
Under the table 5 differential responses condition, the tail gas of catalytic cracked dry gas gating catalytic oxidation hydrogen manufacturing is formed Space Velocity temperature of reaction tail gas and is formed (%) (* 10
-5h
-1) (℃) H
2N
2O
2CO CH
4CO
2H
2+ CO 3.0 500 53.20 7.87 0 34.20 0.55 4.21 87.40 2.0 600 46.50 8.79 0 38.40 1.00 5.26 85.90 1.5 600 43.00 9.50 0 37.30 2.20 8.00 80.30 1.0 820 47.50 8.60 0 37.00 0.81 6.11 84.50
Claims (2)
1. the processing method of an oil refinery dry gas selective oxidation hydrogen manufacturing is characterized in that pressing step:
A. dry gas (1) and oxygen (2) in mixing tank, carry out catalytic selective oxidation reaction (3), and carry out on multi-component Ni-based catalyst in proportion;
B. CO feeds water vapor (5) and carries out synthetic gas transformationreation (6) in the catalysis drying gas after selective oxidation in mixing tank (4);
C. the H in the last dry gas
2Isolate hydrogen (8) and tail gas (9) through transformation absorption or membrane sepn purification (7);
The reaction conditions of step a is: temperature of reaction: 450～950 ℃, and reaction pressure: normal pressure～1MPa, C/O
2=2～1.9, gas reaction air speed: 0.8～3.0 * 10
5h
-1
2. by the described method of claim 1, it is characterized in that adopting among the step a fixed bed or fluidized-bed with oil refinery dry gas optionally catalyzed oxidation be CO and H
2
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113758A CN1095440C (en) | 1998-02-12 | 1998-02-12 | Hydrogen-making process of dry-gas selective catalyst oxidation for oil refinery |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98113758A CN1095440C (en) | 1998-02-12 | 1998-02-12 | Hydrogen-making process of dry-gas selective catalyst oxidation for oil refinery |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1225895A CN1225895A (en) | 1999-08-18 |
| CN1095440C true CN1095440C (en) | 2002-12-04 |
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ID=5223459
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN98113758A Expired - Fee Related CN1095440C (en) | 1998-02-12 | 1998-02-12 | Hydrogen-making process of dry-gas selective catalyst oxidation for oil refinery |
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Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101239702B (en) * | 2008-03-18 | 2010-06-23 | 上海大学 | High temperature coke oven crude gas hydrogen generating system device and technique |
| CN102093157A (en) * | 2009-12-09 | 2011-06-15 | 中国科学院兰州化学物理研究所 | Joint process for preparing ethylene and synthesis gas by direct conversion of methane |
| CN102614764B (en) * | 2011-01-27 | 2014-03-26 | 中科合成油工程有限公司 | Method for processing Fischer-Tropsch synthesis tail gas |
| CN103776040B (en) * | 2012-10-24 | 2015-11-18 | 中国石油化工股份有限公司 | A kind for the treatment of by catalytic oxidation of oil refinery dry gas |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0533232A1 (en) * | 1991-09-20 | 1993-03-24 | METALLGESELLSCHAFT Aktiengesellschaft | Method for generation of hydrogen from raw gas obtained by gasification of solid, liquid or gaseous fuels |
| CN1085821A (en) * | 1992-10-19 | 1994-04-27 | 中国科学院大连化学物理研究所 | A kind of from catalytic cracked dry gas the method for separating hydrocarbon |
| CN1092696A (en) * | 1993-03-24 | 1994-09-28 | 中国石油化工总公司 | Device with membrane separation technique recover hydrogen from catalysis drying gas |
-
1998
- 1998-02-12 CN CN98113758A patent/CN1095440C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0533232A1 (en) * | 1991-09-20 | 1993-03-24 | METALLGESELLSCHAFT Aktiengesellschaft | Method for generation of hydrogen from raw gas obtained by gasification of solid, liquid or gaseous fuels |
| CN1085821A (en) * | 1992-10-19 | 1994-04-27 | 中国科学院大连化学物理研究所 | A kind of from catalytic cracked dry gas the method for separating hydrocarbon |
| CN1092696A (en) * | 1993-03-24 | 1994-09-28 | 中国石油化工总公司 | Device with membrane separation technique recover hydrogen from catalysis drying gas |
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| CN1225895A (en) | 1999-08-18 |
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