CN100377990C - Sulfur-tolerant deoxygenation method for low temperature methanol cleaning process - Google Patents
Sulfur-tolerant deoxygenation method for low temperature methanol cleaning process Download PDFInfo
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- CN100377990C CN100377990C CNB2006100196224A CN200610019622A CN100377990C CN 100377990 C CN100377990 C CN 100377990C CN B2006100196224 A CNB2006100196224 A CN B2006100196224A CN 200610019622 A CN200610019622 A CN 200610019622A CN 100377990 C CN100377990 C CN 100377990C
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Abstract
The present invention provides one sulfur-tolerant deoxidization and low temperature methanol cleaning method, and the method is suitable for low temperature methanol cleaning process of coke gas as material for preparing chemical material gas. Coke gas is first wet purified to eliminate H2S, tar, naphthalene, etc, then heated to 100-420 deg.c at 0.1-10 MPa pressure and deoxidized with sulfur-tolerant deoxidizing agent in deoxidizing tower to oxygen content lower than 10 ppm, and finally purified deeply through low temperature methanol washing to obtain refined chemical material gas. The method is simple and no corrosion to low temperature methanol cleaning.
Description
Technical field
The present invention relates to protect the sulfur-tolerance deoxidation method of low-temperature rectisol purification process.Being particularly related to the coke(oven)gas is the sulfur-tolerance deoxidation method that raw material, employing low-temperature rectisol purification process are produced the material gas process.
Background technology
The by product coke(oven)gas that the required coke of Steel Plant produces in process of coking contain about 50% hydrogen and based on the hydrocarbons of methane, ethene.Utilize coke(oven)gas to produce syngas for synthetic ammonia two kinds of methods are generally arranged: a kind of is to utilize the desulfurization of iron-molybdic catalyst string high temperature oxidation zinc, employing partial oxidation of methane or hydrogen manufacturing of steam reforming technology and carbon monoxide, carry out middle temperature transformation, low temperature shift, decarburization and methanation operation then successively, promptly produce qualified syngas for synthetic ammonia with hot method purification process; Another kind is that the deep refrigeration method makes various hydrocarbons condensations and separates with hydrogen, and then mixes with purity nitrogen and make hydrogen nitrogen mixed gas.Impurity such as coke(oven)gas is coal-tar middle oil, H2S, oxygen need pre-treatment before cryogenic liquefaction separates, and this method is called the cold process purification process.The low-temperature rectisol purification process that the present invention relates to belongs to the cold process purification process.
It is that raw material is produced synthetic ammonia and urea that Benxi Beifang Coal Chemical Co., Ltd. adopts the coke(oven)gas of Benxi North Platform iron and steel (group) limited liability company.Tar in the coke(oven)gas, naphthalene, H
2S all can adopt corresponding method to remove micro-H
2S and organic sulfide need to remove in the low-temperature rectisol purification process.Oxygen has corrosion to low-temperature rectisol purification equipment, needs to be removed to before coke(oven)gas enters the low-temperature rectisol purification process≤10ppm.Both at home and abroad the reductor of existing industrial application all is an anti-sulphur not, and sulfur-tolerance deoxidation is the important difficult problem of domestic and international deoxy technology.
Summary of the invention
Purpose of the present invention will overcome above-mentioned technical barrier exactly, and a kind of effectively and economically sulfur-tolerance deoxidation method is provided, and solves the etching problem that low-temperature rectisol purifies equipment.
The technical scheme that reaches the object of the invention is: a kind of sulfur-tolerance deoxidation method of protecting the low-temperature rectisol purification process, this method are applicable to the coke(oven)gas to be raw material, adopt the low-temperature rectisol purification process to produce the material gas process.Coke(oven)gas removes H by wet method earlier
2S, decoking wet goods and take off the naphthalene primary purifying, after being heated to 100～420 ℃ under the condition of 0.1～10 MPa, enter the deoxidation tower, through sulfur-proof deoxidizing agent with the oxygen removal in the coke(oven)gas to≤10ppm, enter again low-temperature rectisol with the coke(oven)gas deep purifying, be refined into material gas, use for the downstream production process.With make qualified hydrogen nitrogen mixed gas after purity nitrogen mixes, as the unstripped gas of synthetic ammonia.
It is made of the sulfur-proof deoxidizing agent that loads in the described deoxidation tower carrier and deoxy activity component,
Wherein, described carrier is spherical gamma-Al
2O
3, spherical diameter 3-6 millimeter, water-intake rate 50%-100% (volume percent), specific surface area 150-350 rice
2/ gram, physical strength 〉=25 newton/;
Said deoxy activity component is by molybdenum, and cobalt is or/and nickel, and zinc, potassium is or/and sodium, the composition that oxygen and element sulphur constitute, and its general formula is expressed as: MoX
aAX
bBX
cCX
d
In the formula: Mo---molybdenum;
X is oxygen or sulphur, or oxygen sulphur mixture; A=1.0,1.5,2.0 or 2.5;
A is cobalt or nickel, or cobalt nickel mixture; B=1.0,1.5,2.0,2.5 or 3.0;
B is a zinc; C=1.0,1.5 or 2.0;
C is potassium or sodium, or potassium sodium mixture; D=0.5 or 1.0;
The per-cent that said deoxy activity component accounts for the sulfur-proof deoxidizing agent total mass is 10%-40%, and all the other are carrier;
In the said sulfur-proof deoxidizing agent, the mass percent compositing range of deoxy activity component is:
Mo：10％-50％；A：0.1％-30％；
B：0-20％； C：0.1％-20％；
O：0-40％； S：0-40％。
The preparation method of described sulfur-proof deoxidizing agent comprises the steps:
The preparation of the homogeneous phase solution of step 1, deoxy activity component: the soluble compound that takes by weighing described element by active constituent molybdenum, cobalt, nickel, zinc, potassium and sodium element proportioning in the sulfur-proof deoxidizing agent is dissolved in the water, and adding mass concentration is 10%NH
3The aqueous solution is regulated pH=9-12, makes the steeping fluid of active constituent;
The dipping of step 2, deoxy activity component: the carrier that will choose impregnated in respectively in the active constituent steeping fluid that step 1 makes, and floods 4-10 hour;
Step 3, drying and roasting: the carrier that step 2 dipping is got well descended dry 4-10 hour at 60-150 ℃, carried out under 300-500 ℃ roasting 4-8 hour, promptly made sulfur-proof deoxidizing agent.
Described sulfur-proof deoxidizing agent is hydrogen content 0.5%～20%, hydrogen sulfide content 0-2.0% in volume percent, surplus is in the mixed gas of nitrogen, be warmed up to 200～500 ℃ with 5～10 ℃ temperature rise rate per hour gradually by normal temperature and activate, handled 10-40 hour; 100～420 ℃ of temperature of reaction, reaction pressure is normal pressure～1.0 MPas, gas space velocity 1000～3000 hours
-1Condition under sulfur-resistant catalytic deoxidization.
It is 200～400 ℃ that described sulfur-proof deoxidizing agent uses the operation preferred temperature.
Described sulfur-tolerance deoxidation reaction: H
2+ 1/2 O
2=H
2O
Not only tentatively solved the technical barrier of domestic and international sulfur-tolerance deoxidation after the technology implementation of the present invention, also solved the etching problem of oxygen, can guarantee the long-period stable operation of low-temperature rectisol purification process low-temperature rectisol purification equipment.
Description of drawings
Fig. 1 is the sulfur-tolerance deoxidation method process flow diagram of protection low-temperature rectisol purification process of the present invention.
Among the figure coke(oven)gas from detar, take off naphthalene, wet method is taken off H
2Primary purifying operations such as S earlier through being heated to 100～420 ℃, enter deoxidation tower A and deoxidation B respectively more successively, and oxygen in the coke(oven)gas is taken off to≤10ppm, and finally entering low-temperature rectisol, to carry out deep purifying refining.Whole sulfur-tolerance deoxidation process is carried out under the condition of 100～420 ℃ of temperature and pressure 0.1～10 MPa.
Embodiment
For investigating the performance of sulfur-proof deoxidizing agent, colliery chemical industry company limited has carried out coke(oven)gas industry spot lateral flow assay in the north, Benxi:
Method is to adopt the sulfur-bearing coke(oven)gas to enter the isothermal reactor of the sulfur-proof deoxidizing agent that the Hubei Inst. of Chemistry development is housed through heating, reactor is imported and exported the DH-3 type trace oxygen analyzer that oxygen analysis adopts Nanjing analytical instrument limited liability company, coke(oven)gas composition and H
2S content adopts chromatography analysis by Benxi Beifang Coal Chemical Co., Ltd., and organic sulfur content is analyzed by Hubei Inst. of Chemistry development and commercially available more than 10 years HC-2 trace sulfur analyzer.
Coke(oven)gas composition volume percentage composition: CO
22%-3%, O
20.5%-1.0%, CO 8%-12%, H
255%-65%, CH
418%-25%, N
22%-3%, C
mH
n1.5%-2.5%, H
2S 0.2%-0.4%, organosulfur～100 * 10
-6
Sulfur-proof deoxidizing agent granularity Φ 3～5mm, air speed 1000 hours
-1, testing data is listed in the table below.
Coke(oven)gas lateral flow assay micro amount of oxygen analytical data
| Temperature (℃) | Air speed (hour -1) | Inlet oxygen (ppm) | Outlet oxygen (ppm) |
| 400 | 1000 | 9000 | 1.6 |
| 400 | 1000 | 9000 | 1.1 |
| 400 | 1000 | 9000 | 0.8 |
| 350 | 1000 | 9000 | 1.3 |
| 350 | 1000 | 7500 | 1.8 |
| 350 | 1000 | 7500 | 1.6 |
| 300 | 1000 | 7500 | 2.3 |
| 300 | 1000 | 8000 | 2.9 |
| 250 | 1000 | 8000 | 2.2 |
| 250 | 1000 | 8000 | 3.1 |
| 250 | 1000 | 8000 | 3.8 |
| 250 | 1000 | 8000 | 3.1 |
| 250 | 1000 | 8000 | 4.0 |
| 250 | 1000 | 9000 | 3.1 |
| 250 | 1000 | 7500 | 3.5 |
| 250 | 1000 | 7500 | 3.4 |
| 250 | 1000 | 7500 | 3.5 |
| 250 | 1000 | 5000 | 3.8 |
| 200 | 1000 | 5000 | 4.5 |
| 200 | 1000 | 9000 | 4.7 |
Claims (3)
1. a sulfur-tolerance deoxidation method of protecting the low-temperature rectisol purification process is that raw material, employing low-temperature rectisol purification process are produced material gas with the coke(oven)gas, and it is characterized in that: coke(oven)gas removes H by wet method earlier
2S, detar and take off the naphthalene primary purifying after, be to be heated under the condition of 0.1～10 MPa to enter the deoxidation tower that sulfur-proof deoxidizing agent is housed after 100～420 ℃ at pressure, with the O in the coke(oven)gas
2Take off to≤10ppm, enter again low-temperature rectisol with the coke(oven)gas deep purifying, be refined into material gas, use for the downstream production process, described sulfur-proof deoxidizing agent is made of carrier and deoxy activity component, wherein said carrier is spherical gamma-Al
2O
3, spherical diameter 3-6 millimeter, volume water absorption rate 50%-100%, specific surface area 150-350 rice
2/ gram, physical strength 〉=25 newton/;
Described deoxy activity component is by molybdenum, and cobalt is or/and nickel, and zinc, potassium is or/and sodium, the composition that oxygen and element sulphur constitute, and its general formula is expressed as: MoX
aAX
bBX
cCX
d
In the formula: Mo---molybdenum;
X is oxygen or sulphur, or oxygen sulphur mixture; A=1.0,1.5,2.0 or 2.5;
A is cobalt or nickel, or cobalt nickel mixture; B=1.0,1.5,2.0,2.5 or 3.0;
B is a zinc; C=1.0,1.5 or 2.0;
C is potassium or sodium, or potassium sodium mixture; D=0.5 or 1.0;
The per-cent that described deoxy activity component accounts for the sulfur-proof deoxidizing agent total mass is 10%-40%, and all the other are carrier;
In the described sulfur-proof deoxidizing agent, the mass percent compositing range of deoxy activity component is:
Mo：10％-50％； A：0.1％-30％；
B：0-20％； C：0.1-20％；
O：0-40％； S：0-40％；
The sulfur-proof deoxidizing agent use temperature is 100～420 ℃.
2. the sulfur-tolerance deoxidation method of protection low-temperature rectisol purification process as claimed in claim 1 is characterized in that: the sulfur-tolerance deoxidation process is carried out under the condition of 100～420 ℃ of temperature in the deoxidation tower.
3. the sulfur-tolerance deoxidation method of protection low-temperature rectisol purification process as claimed in claim 1 is characterized in that: the sulfur-tolerance deoxidation process is carried out under the condition of 200～400 ℃ of temperature in the deoxidation tower.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100196224A CN100377990C (en) | 2006-07-13 | 2006-07-13 | Sulfur-tolerant deoxygenation method for low temperature methanol cleaning process |
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|---|---|---|---|
| CNB2006100196224A CN100377990C (en) | 2006-07-13 | 2006-07-13 | Sulfur-tolerant deoxygenation method for low temperature methanol cleaning process |
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| Publication Number | Publication Date |
|---|---|
| CN1887690A CN1887690A (en) | 2007-01-03 |
| CN100377990C true CN100377990C (en) | 2008-04-02 |
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ID=37576969
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104178229B (en) * | 2014-08-01 | 2016-07-06 | 张秦龙 | A kind of gas cleaning system |
| CN107841759A (en) * | 2017-09-25 | 2018-03-27 | 杨家华 | Low-temp methanol washs oxygenerator |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1463801A (en) * | 2002-06-12 | 2003-12-31 | 中国石化集团齐鲁石油化工公司 | Low cost sulfur transformation resistant deoxidizing agent |
| CN1473911A (en) * | 2003-08-06 | 2004-02-11 | 湖北省化学研究院 | Organic sulfur removing and deoxygenation process for producing high pruity CO gas |
| CN1724155A (en) * | 2005-06-20 | 2006-01-25 | 天津化工研究设计院 | Sulphur resisting catalyzing deoxidation agent and its production process |
-
2006
- 2006-07-13 CN CNB2006100196224A patent/CN100377990C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1463801A (en) * | 2002-06-12 | 2003-12-31 | 中国石化集团齐鲁石油化工公司 | Low cost sulfur transformation resistant deoxidizing agent |
| CN1473911A (en) * | 2003-08-06 | 2004-02-11 | 湖北省化学研究院 | Organic sulfur removing and deoxygenation process for producing high pruity CO gas |
| CN1724155A (en) * | 2005-06-20 | 2006-01-25 | 天津化工研究设计院 | Sulphur resisting catalyzing deoxidation agent and its production process |
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Address after: Zip code, Bei Tai town, Pingshan District, Benxi, Liaoning, China: 117017 Co-patentee after: Huashuo Technology Co., Ltd. Patentee after: Benxi North Coal Chemical Co., Ltd. Address before: Zip code, Bei Tai town, Pingshan District, Benxi, Liaoning, China: 117017 Co-patentee before: Hubei Prov. Inst. of Chemistry Patentee before: Benxi North Coal Chemical Co., Ltd. |