CN1046213C - Normal temperature zinc oxide desulfurizer and preparation method thereof - Google Patents
Normal temperature zinc oxide desulfurizer and preparation method thereof Download PDFInfo
- Publication number
- CN1046213C CN1046213C CN 93111222 CN93111222A CN1046213C CN 1046213 C CN1046213 C CN 1046213C CN 93111222 CN93111222 CN 93111222 CN 93111222 A CN93111222 A CN 93111222A CN 1046213 C CN1046213 C CN 1046213C
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- zno
- agent
- zinc
- acid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims description 58
- 239000011787 zinc oxide Substances 0.000 title claims description 29
- 238000002360 preparation method Methods 0.000 title claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 16
- 239000004568 cement Substances 0.000 claims abstract description 7
- 229910052742 iron Inorganic materials 0.000 claims abstract description 7
- 239000011344 liquid material Substances 0.000 claims abstract 2
- 235000003599 food sweetener Nutrition 0.000 claims description 24
- 239000003765 sweetening agent Substances 0.000 claims description 24
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 238000006477 desulfuration reaction Methods 0.000 claims description 10
- UOURRHZRLGCVDA-UHFFFAOYSA-D pentazinc;dicarbonate;hexahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[Zn+2].[O-]C([O-])=O.[O-]C([O-])=O UOURRHZRLGCVDA-UHFFFAOYSA-D 0.000 claims description 9
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000000292 calcium oxide Substances 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 238000000465 moulding Methods 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 3
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 3
- 235000010755 mineral Nutrition 0.000 claims description 3
- 239000011707 mineral Substances 0.000 claims description 3
- 150000007524 organic acids Chemical class 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- FMRLDPWIRHBCCC-UHFFFAOYSA-L Zinc carbonate Chemical compound [Zn+2].[O-]C([O-])=O FMRLDPWIRHBCCC-UHFFFAOYSA-L 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 239000011667 zinc carbonate Substances 0.000 claims description 2
- 235000004416 zinc carbonate Nutrition 0.000 claims description 2
- 229910000010 zinc carbonate Inorganic materials 0.000 claims description 2
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 claims description 2
- 229940007718 zinc hydroxide Drugs 0.000 claims description 2
- 229910021511 zinc hydroxide Inorganic materials 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052717 sulfur Inorganic materials 0.000 abstract description 10
- 239000011593 sulfur Substances 0.000 abstract description 10
- 230000000694 effects Effects 0.000 abstract description 3
- 238000002156 mixing Methods 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 230000003009 desulfurizing effect Effects 0.000 abstract 1
- 239000007789 gas Substances 0.000 description 9
- 238000012360 testing method Methods 0.000 description 8
- 230000023556 desulfurization Effects 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 229930195733 hydrocarbon Natural products 0.000 description 2
- 150000002430 hydrocarbons Chemical class 0.000 description 2
- 238000004898 kneading Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
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- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
A normal-temp desulfurizing agent of gaseous or liquid material containing S is prepared from the main raw materials ZnO and structural assistant (iron cement) through mixing at 0-200 deg.C and 0.1-6.0MPa, and features higher activity (increased by 30-50%) and sulfur capacity (increased by 30% or more).
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 the smart desulfurization of various petrochemical materials gas, industrial gas, has 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 discloses a kind of normal temp zinc oxide desulfuriging agent, and its use temperature is lower, has 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 more than 80～95% (m/m).Zinc oxide in the sweetening agent can be the form adding with zinc oxide, zinc hydroxide, zinc carbonate or zinc subcarbonate, wherein add best with ZnO and zinc subcarbonate form, and zinc oxide accounts for 10～50% (m/m), and zinc subcarbonate accounts for 90～50% (m/m) for best.Structural promoter among the present invention adopts the iron aluminous cement, mainly is CaO, Fe
2O
3, Al
2O
3Deng mixture, CaO content is 0.5～5.0% (m/m), Fe in the finished product sweetening agent
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 1～10% (m/m) of siccative, extrusion, drying, roasting make the finished product sweetening agent according to a conventional method then, and it consists of: ZnO80～95% (m/m), CaO0.5～5.0% (m/m), Fe
2O
30.5～5.0% (m/m), Al
2O
30.5～5.0% (m/m).
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 the smart desulfurization of various sulfurous gass such as hydrogen, coal gas, synthetic gas, gaseous hydrocarbons, liquefied hydrocarbon.Its use temperature can be in 0～200 ℃ of scope, applying pressure 0.1～6.0Mpa (absolute pressure).
The invention effect:
The 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 is high by 30～50%, tests as follows:
Sweetening agent of the present invention and external like product Britain product compare test:
Test conditions: 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 15000ppm
Outlet H
2S 0.05ppm
Test has investigated 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
| Air speed h -1Sulfur capacity % (m/m) sweetening agent | 1500 | 3000 | 4500 | 6000 |
| Sweetening agent of the present invention | 8.2 | 7.6 | 6.8 | 6.2 |
| Britain's product | 5.7 | 5.3 | 4.6 | 4.3 |
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.
Sulfur capacity under two kinds of sweetening agent differing tempss of table 2.
| Temperature Sulfur capacity % (m/m) sweetening agent | 20℃ | 50℃ | 80℃ |
| Sweetening agent of the present invention | 8.6 | 10.8 | 11.7 |
| Britain's product | 5.9 | 8.3 | 9.4 |
In the double-column in series desulfurization test, the doctor solution consumption of each reactor is 70ml, total air speed 1200h
-1, unstripped gas is industrial synthetic gas, allocates the H of 5000ppm into
2S, 20 ℃ of temperature of reaction, normal pressure is operation down, contains the steam of 1.6% (m/m) in the unstripped gas.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, off-test.Record the Sulfur capacity of each reactor with ordinary method, the result is as shown in table 3:
Table 3. double tower test Sulfur capacity data
| Sweetening agent | Sweetening agent of the present invention | Britain's product | ||
| Reactor | First reactor | Second reactor | First reactor | Second reactor |
| Sulfur capacity % (m/m) | 12.39 | 3.59 | 9.35 | 2.11 |
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
Zinc subcarbonate 90 grams, zinc oxide 10 grams, iron cement 13 grams are done mixed back and are added formic acid 2 grams, and water is an amount of, mediates, and behind the extruded moulding, drying, roasting promptly get ambient temperature desulfuration agent.
Embodiment 2
Zinc subcarbonate 80 grams, zinc oxide 20 grams, iron aluminous cement 10 grams, the dried back of mixing adds citric acid 5 grams, and water is an amount of, and behind kneading, extruded moulding, dry again, roasting promptly get ambient temperature desulfuration agent.
Embodiment 3
Zinc subcarbonate 60 grams, zinc oxide 40 grams, iron aluminous cement 8 grams are done mixed back and are added formic acid 2 grams, citric acid 4 grams, and water is an amount of, and behind kneading, the extruded moulding, drying, roasting more promptly gets ambient temperature desulfuration agent.
Claims (8)
1. a sweetening agent of handling various sulfurous gass, liquid material belongs to normal temp zinc oxide desulfuriging agent, it is characterized in that:
Consist of: ZnO 80～95% (m/m)
CaO 0.5～5％(m/m)
Fe
2O
3 0.5～5％(m/m)
Al
2O
3 0.5～5％(m/m)
Condition is: said components content sum is 100%.
2. the preparation method of an ambient temperature desulfuration agent, main component is ZnO, it is characterized in that: the main component ZnO80-95% (m/m) and the structural promoter iron aluminous cement 5-20% (m/m) of catalyzer are mixed, form through extruded moulding, drying, roasting again.
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 is a kind of mineral acid or two or more mixtures, or a kind of organic acid or two or more mixtures, and add-on is 1～10% (m/m) of total dry material.
4. by the described method of claim 2, it is characterized in that described zinc oxide is 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 mineral acid is a nitric acid, described organic acid is formic acid, acetate, oxalic acid or citric acid.
6. by the described method of claim 2, it is characterized in that the composition of described iron aluminous cement comprises CaO, Fe
2O
3, Al
2O
3
7. by the described method of claim 2, it is characterized in that described ZnO is the form adding with ZnO and zinc subcarbonate.
8. by the described method of claim 2, it is characterized in that described ZnO, wherein zinc oxide accounts for 10～50% (m/m), and zinc subcarbonate accounts for 90～50% (m/m).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93111222 CN1046213C (en) | 1993-04-26 | 1993-04-26 | Normal temperature zinc oxide desulfurizer and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 93111222 CN1046213C (en) | 1993-04-26 | 1993-04-26 | Normal temperature zinc oxide desulfurizer and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1094331A CN1094331A (en) | 1994-11-02 |
| CN1046213C true 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 temperature zinc oxide desulfurizer and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1046213C (en) |
Cited By (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 normal temperature desulfurizer |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2177769C (en) * | 1995-06-07 | 1999-08-24 | Gyanesh P. Khare | Particulate compositions that comprise zinc aluminate |
| US5710091A (en) * | 1995-06-07 | 1998-01-20 | Phillips Petroleum Company | Sorbent compositions |
| US8137655B2 (en) * | 2008-04-29 | 2012-03-20 | Enerkem Inc. | Production and conditioning of synthesis gas obtained from biomass |
| FR2940967B1 (en) * | 2009-01-12 | 2012-07-20 | Inst Francais Du Petrole | PREPARATION OF A ZINC OXIDE-BASED SOLID FOR THE PURIFICATION OF 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 |
| 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 |
| 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 | A kind of preparation method of zinc oxide desulfurizer |
-
1993
- 1993-04-26 CN CN 93111222 patent/CN1046213C/en not_active Expired - Fee Related
Cited By (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 normal temperature desulfurizer |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1094331A (en) | 1994-11-02 |
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