CN1094331A - Normal temp zinc oxide desulfuriging agent and preparation method - Google Patents
Normal temp zinc oxide desulfuriging agent and preparation method Download PDFInfo
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- CN1094331A CN1094331A CN 93111222 CN93111222A CN1094331A CN 1094331 A CN1094331 A CN 1094331A CN 93111222 CN93111222 CN 93111222 CN 93111222 A CN93111222 A CN 93111222A CN 1094331 A CN1094331 A CN 1094331A
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Abstract
The normal temperature ZnO sweetening agent of a kind of gaseous state of sulfur-bearing, liquid material, 0-200 ℃ of use temperatures, applying pressure 0.1-6.0MPa (absolute pressure) is that iron cement mixes by main raw material ZnO and structural promoter, the specific activity prior art of this sweetening agent improves 30-50%, and Sulfur capacity improves more than 30%.
Description
The present invention relates to a kind of novel normal-temperature Zinc oxide desulfurizer in the petrochemical industry.
Zinc oxide desulfurizer is widely used in various petrochemical materials gas, the smart desulfurization of industrial gas.Having characteristics such as desulfurization precision height, Sulfur capacity be big, is the product of comparative maturity.At present the commodity Zinc oxide desulfurizer mainly contains two kinds of high temperature modification and low temperature modifications, and the former use temperature is 350-400 ℃, and latter's use temperature is 180-250 ℃.Because two types sweetening agent all needs to use at a certain temperature, needs thermal source, and consumes certain energy; Sweetening agent also can play certain katalysis simultaneously, and some side reactions take place.In order to overcome above-mentioned shortcoming, carried out the development of normal temp zinc oxide desulfuriging agent in recent years in the world, European patent 279116; 207645; 230146 disclose a kind of normal temp zinc oxide desulfuriging agent, and its use temperature is lower, have certain low temperature active.But it is relatively poor that its weak point is an intensity, and point is pressed and only is 28N/, and low temperature active is on the low side, and the life-span is shorter, and use cost is higher.
The present invention seeks to develop a kind of novel normal-temperature Zinc oxide desulfurizer with higher low temperature active and higher-strength.
A kind of normal temp zinc oxide desulfuriging agent of the present invention's development is by ZnO, CaO, Fe
2O
3, Al
2O
3Deng composition, active ingredient ZnO, its content is at 80-95%(m/m) more than.Zinc oxide in the sweetening agent can be to add with the form of zinc oxide, zinc hydroxide, zinc carbonate or zinc subcarbonate, wherein adds preferably with ZnO and zinc subcarbonate form, and zinc oxide accounts for 10-50%, and zinc subcarbonate accounts for 90-50%(wt) for best.Structural promoter among the present invention adopts iron cement, mainly is CaO, Fe
2O
3, Al
2O
3Deng mixture, CaO content is 0.5-5.0%(m/m in the finished product sweetening agent), Fe
2O
3Be 0.5-5.0%(m/m), Al
2O
3Be 0.5-5.0%(m/m).
For intensity and the activity that improves sweetening agent, after mixing, above-mentioned raw materials added a kind of peptizing agent.This peptizing agent can be a kind of mineral acid, as nitric acid; Also can be a kind of organic acid or two or more mixtures, as formic acid, acetate, oxalic acid, citric acid etc.Its add-on is the 1-10%(m/m of siccative).CaO 0.5-5.0%(mm ZnO 80-95%(mm)), Fe extrusion, drying, roasting make the finished product sweetening agent according to a conventional method then, and it consists of:
2O
30.5-5.0%(mm), Al
2O
30.5-5.0%(mm).
Crushing strength 〉=the 60N/cm of finished product sweetening agent of the present invention, specific surface are 60-85m
2/ g, specific pore volume＞0.5ml/g.
This sweetening agent can be applicable to hydrogen, coal gas, synthetic gas, gaseous hydrocarbons, the smart desulfurization of various sulfurous gass such as liquefied hydrocarbon.Its use temperature can be in 0-200 ℃ of scope, applying pressure 0.1-6.0MPa(absolute pressure).
The effect of invention:
The high 30-50% of low temperature active of the more present commercially available normal temp zinc oxide desulfuriging agent of low temperature active of sweetening agent of the present invention, test as follows:
Sweetening agent of the present invention and external like product Britain product compare test:
Experiment condition: doctor solution consumption 0.8ml,
20 ℃ of temperature of reaction, pressure are normal pressure,
Unstripped gas consists of H
2.H
2S, inlet H
2S 15000P, P, M
Outlet H
2S＜0.05P, P, M
The effects 1500,3000,4500,6000h
-1Desulfurization situation under four air speed conditions, the result is as shown in table 1:
Sulfur capacity during two kinds of sweetening agents differences of table 1 air speed
The desulfurization performance of two kinds of sweetening agents in the time of 20 ℃, 50 ℃, 80 ℃ also investigated in test, and wherein air speed is 3000h
-1, the unstripped gas moisture content is 2.3%(m/m).The result is as shown in table 2.
Table 2: the Sulfur capacity under two kinds of sweetening agent differing tempss
In the double-column in series desulfurization, the doctor solution consumption of each reactor is 70ml.Total air speed 1200h
-1Unstripped gas is industrial synthetic gas, allocates the H of 5000PPM into
2S.20 ℃ of temperature of reaction, normal pressure is operation down.Contain 1.6%(m/m in the unstripped gas) steam.Reactor used is the Glass tubing of internal diameter 28mm.Desulfidation tail gas control H
2S content is less than 0.05PPM.As outlet H
2When S content surpasses 0.05PPM, think that promptly sweetening agent penetrates, experiment finishes.Record the Sulfur capacity of each reactor with ordinary method, the result is as shown in table 3.
Table 3: double tower experiment Sulfur capacity data
From table 1, table 2, the table 3 Sulfur capacity height of sweetening agent of the present invention as can be seen, promptly active high,
The intensity of sweetening agent of the present invention is also than prior art height.
Embodiment 1
90 parts of zinc subcarbonates, 10 parts in zinc oxide, 13 parts of iron cements after dried the mixing, add formic acid 2g, and water is an amount of, mediates, and behind the extruded moulding, drying, roasting promptly get ambient temperature desulfuration agent.
Embodiment 2
80 parts of zinc subcarbonates, 20 parts in zinc oxide, 10 parts of iron cements after dried the mixing, add citric acid 5g, and water is an amount of, and through mediating, behind the extruded moulding, dry again, roasting promptly get ambient temperature desulfuration agent.
Embodiment 3
60 parts of zinc subcarbonates, 40 parts in zinc oxide, 8 parts of iron cements after dried the mixing, add formic acid 2g, citric acid 4g, water is an amount of.Mediate, behind the extruded moulding, drying, roasting more promptly gets ambient temperature desulfuration agent.
Claims (9)
1, a kind of sweetening agent that is used to handle various sulfurous gass, liquid material belongs to normal temp zinc oxide desulfuriging agent, it is characterized in that:
A forms: ZnO 80-95% (m/m)
CaO 0.5-5%(m/m)
Fe
2O
30.5-5%(m/m)
Al
2O
30.5-5%(m/m)
2, a kind of preparation method of ambient temperature desulfuration agent, major ingredient is ZnO, it is characterized in that: the structural promoter iron cement 5-20% of major ingredient ZnO80-95% and catalyzer is mixed, and again through extruded moulding, dry, roasting forms.
3, by the described method of claim 2, it is characterized in that in ZnO sweetening agent preparation process, adding a kind of peptizing agent, this peptizing agent can be a kind of mineral acid or two or more mixtures, also can be a kind of organic acid or two or more mixtures, and add-on is the 1-10% of total dry material.
4, by the described method of claim 2, it is characterized in that described zinc oxide, can be the form adding with zinc oxide, zinc hydroxide, zinc carbonate or zinc subcarbonate.
5, by the described method of claim 2, it is characterized in that described peptizing agent is mineral acid, can is nitric acid that described organic acid can be formic acid, acetate, oxalic acid, citric acid etc.
6, by the described method of claim 2, it is characterized in that the composition of described iron cement comprises CaO, Fe
2O
3, Al
2O
3Deng.
7, by the described method of claim 2, it is characterized in that described peptizing agent, mineral acid can be a nitric acid, and described organic acid can be formic acid, acetate, oxalic acid, citric acid etc.
8,, it is characterized in that described ZnO adds best with the form of ZnO and zinc subcarbonate by the described method of claim 2.
9, by the described method of claim 2, it is characterized in that described ZnO, wherein ZnO accounts for 10-50%, and it is best that zinc subcarbonate accounts for 90-50%.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93111222 CN1046213C (en) | 1993-04-26 | 1993-04-26 | Normal temp zinc oxide desulfuriging agent and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93111222 CN1046213C (en) | 1993-04-26 | 1993-04-26 | Normal temp zinc oxide desulfuriging agent and its preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1094331A true CN1094331A (en) | 1994-11-02 |
| CN1046213C CN1046213C (en) | 1999-11-10 |
Family
ID=4989024
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 93111222 Expired - Fee Related CN1046213C (en) | 1993-04-26 | 1993-04-26 | Normal temp zinc oxide desulfuriging agent and its preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1046213C (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064273C (en) * | 1995-06-07 | 2001-04-11 | 菲利浦石油公司 | Sorbent compositions |
| CN1064274C (en) * | 1995-06-07 | 2001-04-11 | 菲利浦石油公司 | Particulate compositions |
| CN102015973A (en) * | 2008-04-29 | 2011-04-13 | 埃讷肯公司 | Production and conditioning of synthesis gas obtained from biomass |
| CN102773068A (en) * | 2011-05-11 | 2012-11-14 | 中国石油化工股份有限公司 | Desulfurizing agent and preparation method thereof |
| CN103212369A (en) * | 2012-01-19 | 2013-07-24 | 北京三聚环保新材料股份有限公司 | High-strength ferric hydroxide desulfurizer for normal temperature desulfurization, and preparation method thereof |
| CN102271786B (en) * | 2009-01-12 | 2015-03-25 | Ifp新能源公司 | Preparation of a solid containing zinc oxide used for purifying a gas or a liquid |
| CN104524973A (en) * | 2015-01-16 | 2015-04-22 | 重庆地之净科技有限公司 | Liquefied gas desulfurizing agent |
| CN106609166A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Desulfurizing agent and preparing method thereof |
| CN113372894A (en) * | 2021-06-11 | 2021-09-10 | 四川正蓉上之登科技有限公司 | Efficient and rapid soluble sulfur removal corrosion inhibitor and preparation method thereof |
| CN114272918A (en) * | 2021-12-31 | 2022-04-05 | 辽宁玖号科技有限公司 | Preparation method of zinc oxide desulfurizer |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101288821B (en) * | 2007-04-19 | 2012-09-05 | 北京三聚环保新材料股份有限公司 | Preparation method of calcium zincate and calcium zincate reclaiming agent at normal temperature |
-
1993
- 1993-04-26 CN CN 93111222 patent/CN1046213C/en not_active Expired - Fee Related
Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1064274C (en) * | 1995-06-07 | 2001-04-11 | 菲利浦石油公司 | Particulate compositions |
| CN1064273C (en) * | 1995-06-07 | 2001-04-11 | 菲利浦石油公司 | Sorbent compositions |
| CN102015973A (en) * | 2008-04-29 | 2011-04-13 | 埃讷肯公司 | Production and conditioning of synthesis gas obtained from biomass |
| CN104803675B (en) * | 2009-01-12 | 2020-05-05 | Ifp 新能源公司 | Preparation of zinc oxide-based solids useful for purifying gases or liquids |
| CN102271786B (en) * | 2009-01-12 | 2015-03-25 | Ifp新能源公司 | Preparation of a solid containing zinc oxide used for purifying a gas or a liquid |
| CN104803675A (en) * | 2009-01-12 | 2015-07-29 | Ifp新能源公司 | Preparation of a solid based on zinc oxide for use in purifying a gas or a liquid |
| CN102773068A (en) * | 2011-05-11 | 2012-11-14 | 中国石油化工股份有限公司 | Desulfurizing agent and preparation method thereof |
| CN103212369A (en) * | 2012-01-19 | 2013-07-24 | 北京三聚环保新材料股份有限公司 | High-strength ferric hydroxide desulfurizer for normal temperature desulfurization, and preparation method thereof |
| CN103212369B (en) * | 2012-01-19 | 2016-09-14 | 北京三聚环保新材料股份有限公司 | A kind of high-strength FeOOH desulfurizer of room temperature desulfurization and preparation method thereof |
| CN104524973A (en) * | 2015-01-16 | 2015-04-22 | 重庆地之净科技有限公司 | Liquefied gas desulfurizing agent |
| CN106609166A (en) * | 2015-10-22 | 2017-05-03 | 中国石油化工股份有限公司 | Desulfurizing agent and preparing method thereof |
| CN106609166B (en) * | 2015-10-22 | 2020-09-04 | 中国石油化工股份有限公司 | Desulfurizing agent and preparation method thereof |
| CN113372894A (en) * | 2021-06-11 | 2021-09-10 | 四川正蓉上之登科技有限公司 | Efficient and rapid soluble sulfur removal corrosion inhibitor and preparation method thereof |
| CN114272918A (en) * | 2021-12-31 | 2022-04-05 | 辽宁玖号科技有限公司 | Preparation method of zinc oxide desulfurizer |
Also Published As
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|---|---|
| CN1046213C (en) | 1999-11-10 |
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