CN1966625A - Normal temperature high activity high-sulfur accommodation high-strength desulfurizer production method - Google Patents
Normal temperature high activity high-sulfur accommodation high-strength desulfurizer production method Download PDFInfo
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- CN1966625A CN1966625A CN 200510022065 CN200510022065A CN1966625A CN 1966625 A CN1966625 A CN 1966625A CN 200510022065 CN200510022065 CN 200510022065 CN 200510022065 A CN200510022065 A CN 200510022065A CN 1966625 A CN1966625 A CN 1966625A
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Abstract
The invention relates to a kind of ferric oxide devulcanizing agent with high activity, high sulphur tolerating dosage and high intensity which add 0.01-35% of pore-making agent with volatility and hydrophobicity such as alcohol (spirit or wine), acetic acid (or vinegar), naphtalin, tar, kerosene and vegetable oil to the devulcanizing agent; at the same time, add 0.01-15% of curing agent such as sodium silicate, cement, lime or sodium metasilicate to the material which needs to be kneaded; shape the devulcanizing agent by kneading, squeezing or other methods; dry the devulcanizing agent at ordinary temperature; if dried in the oven, the producers must adopt temperature programming (keep 30-50DEG C for more than 3h; heat to about 80DEG C and keep the temperature for more than 0.5h; finally complete the drying process at 200DEG C.
Description
Technical field:
The present invention relates to a kind of production method of ferric oxide desulfurizer, the ferric oxide desulfurizer that adopts the present invention to produce has higher activity and higher Sulfur capacity, and the abrasive wear resistance height.
Background technology:
In coal gas and selexol process technology, ferric oxide desulfurizer uses very extensive, it has, and Sulfur capacity is higher, price is lower, the desulfurization precision advantage of higher, but its abrasive wear resistance is very undesirable, can only use on the fixed bed desulfurizer of little tolerance, and to the thermopnore desulfurizer of atm number, can't use because its abrasive wear resistance is low at all.
Even the sweetening agent that in the fixed bed desulfurizer of little tolerance, uses, because abrasive wear resistance is low, still there is gas bias current phenomenon after the filling in use, this mainly is because sweetening agent inhomogeneous the causing of filling that efflorescence causes when filling, so the abrasive wear resistance that improves sweetening agent is the inevitable approach that ferric oxide desulfurizer enlarges use range and field.Simultaneously, the other weak point of ferric oxide desulfurizer is to use Sulfur capacity low under the condition of anaerobic, how increasing considerably the Sulfur capacity that ferric oxide desulfurizer uses under oxygen free condition, reduce the priming cost of gas sweetening, is the key of ferric oxide desulfurizer and other type sorbent material, sweetening agent competition.
With respect to Zinc oxide desulfurizer and activated carbon adsorbent, the ferric oxide desulfurizer desulfurization precision is not high, is difficult to the disposable requirement that reaches Chemical Manufacture, has limited it yet and has been to use.
Patent CN98117729.8 discloses a kind of containing with Ca#-[2] Fe#-[2] 0#-[5] be the sweetening agent of active ingredient, and the method for preparing this sweetening agent.The effective active component of the sweetening agent of patent CN01142355.2 invention is six hydration ferrous acid DFP 3CaOFe
2O
36H
2O.Patent CN98117322.5 provides a kind of high-temp sulfur-sensitive ceramic heating gas sweetening agent, it is characterized in that sulfur-sensitive ceramic is a basic raw material with titanium dioxide and zinc oxide, bismuthous oxide bismuth trioxide is a trace mineral supplement, adopts the chemical coprecipitation method preparation, gel slurries spray drying forming, the particle high-temperature calcining.Patent CN91109694.9 provides a kind of sweetening agent and technology with the acid waste liquid preparation, and its major ingredient is ferric oxide and bentonitic mixture.Patent CN00116020.6 provides a kind of hypoxia tolerance composite metal hydrous oxide desulfurizing agent and preparation method.This sweetening agent is by hydrous iron oxide Fe
2O
3H
2The compound of any one or more compound and/or alkali earth metal Ca, Mg is formed among O and other metal element Ti, Co, Ni, Mo, Zn, Cd, Cr, Hg, Cu, Ag, Sn, Pb, the Bi.Patent CN01106879.5 has disclosed a kind of normal temperature iron oxide fine desulfurizer, produces through ferrous sulfate, precipitation agent ammoniacal liquor, yellow soda ash and lime, auxiliary agent nickel or chromium or copper or cadmium or other oxidation of interim metal, tackiness agent and carrier: cement, wood chip.CN200310101695.4 discloses a kind of reproducible sweetening agent and preparation method thereof, this sweetening agent is a kind of the multiple element compound, the ferric oxide or the sponge iron that contain mass ratio 15-80%, the binding agent of mass ratio 0-30%, basic metal-alkaline earth metal oxide of mass ratio 15-80%, the pore-forming material of mass ratio 1-10%, mass ratio 1-5% synergistic agent; The preparation method of this sweetening agent is through pre-treatment, dipping, kneading, moulding, roasting, activation altogether; This preparation method has smart desulfurization and iterative regenerable function.Patent CN00116020.6 discloses a kind of hypoxia tolerance composite metal hydrous oxide desulfurizing agent and preparation.This sweetening agent is by hydrous iron oxide Fe
2O
3H
2O and the hydrous oxide that is selected from any one or more metallic element among Ti, Co, Ni, Mo, Zn, Cd, Cr, Hg, Cu, Ag, Sn, Pb, the Bi, and the mixture of the oxide compound of alkali earth metal Ca, Mg composition.Its method for making is that molysite or ferrous salt are mixed with solution, adds inorganic alkaline thing and excessive in solution, adds the compound of described other metallic element again, optional neutralizes with mineral alkali, through solid-liquid separation, moulding is made, and the compound moulding of optional adding alkali earth metal is made.
The method of these patents does not all add volatility and hydrophobic nature pore-forming material, generally be to add wood chip as pore-forming material, the sweetening agent chad of being made all is a macropore, not only make the activity of sweetening agent be subjected to bigger influence, and the intensity of sweetening agent is also poor, has influenced the use range and the function of ferric oxide desulfurizer.
Summary of the invention:
According to the chemical kinetics principle, specific surface area increases then speed of response increase.The present invention promptly adds pore-forming material to increase the specific surface area of sweetening agent, adds solidifying agent to increase the abrasive wear resistance of sweetening agent.
This patent discloses the sweetening agent production method of a kind of high reactivity, high Sulfur capacity and high abrasion resistance strength, sweetening agent raw material to the needs kneading, add ethanol (alcohol or wine), acetic acid (vinegar), naphthalene, tar, kerosene, vegetables oil or the like volatility and hydrophobic nature pore-forming material, additional proportion is 0.01% to 35%, in the sweetening agent raw material that needs are mediated, add water glass, cement, lime, Starso or the like solidifying agent simultaneously, additional proportion is 0.01% to 15%, fully mediate then, the kneading time is 1 minute to 10 hours, to mediate 30 minutes for well.
After the kneading, material is shaped to Φ 2mm to Φ 8mm through extrusion or other method, carries out drying again, and drying means is to adopt to dry at normal temperatures to good.If through heating, drying, then need to adopt temperature-programmed mode, temperature programming is 30～50 ℃ low-temperature zone constant temperature 1 to 10 hour, is warmed up to middle-temperature section constant temperature about 80 ℃ again more than 0.5 hour, finishes drying below 200 ℃ at last.
The volatility pore-forming material be at normal temperatures easily volatilization be the solid of gas, liquid, they are to sweetening agent formation pore-creating effect, can add wherein a kind of, also can add wherein multiple.According to test, the volatility pore-forming material cooperates for best according to arbitrary proportion with wherein a kind of of methyl alcohol, ethanol (alcohol or wine) or two kinds.
The hydrophobic nature pore-forming material cooperates for best according to arbitrary proportion with wherein a kind of of naphthalene, kerosene, vegetables oil or three kinds.
Volatility pore-forming material and hydrophobic nature pore-forming material can add in same sweetening agent kind simultaneously, the ratio that adds can be any ratio, but it is best having volatile pore-forming material naphthalene concurrently with hydrophobic nature, and the sweetening agent drying that contains the naphthalene pore-forming material need be heated to more than 150 ℃.
Solidifying agent water glass, cement, lime, Starso can add in same sweetening agent kind simultaneously, and the ratio of adding can be any ratio, also can be wherein a kind of.
Through test, the crucial physical and chemical index of sweetening agent is after adding pore-forming material and the solidifying agent
Specific surface: 160-320m
2/ g
Bulk density: 0.46-0.64Kg/L
Intensity: 〉=80N/cm is generally 95N/cm
The work Sulfur capacity: 〉=24%, be generally 36% (w.)
Embodiment:
Embodiment 1:
The production and the applicable cases of certain Steel Plant's coke oven gas desulfurization agent
Produce the sweetening agent raw material: be crushed to the following ferric oxide 38% of 300 orders, ethanol 1%, naphthalene 0.5%, lime 6%, all the other are stopping composition.
Mediating 50 minutes kneading time after the above raw material mixing.
After the kneading, material is shaped to the strip of Φ 5mm through extrusion or other method, 30～50 ℃ low-temperature zone constant temperature 2 hours, is warmed up to middle-temperature section constant temperature about 80 ℃ again more than 1 hour, finishes drying at 150 ℃ at last.
Through test, the crucial physical and chemical index of this sweetening agent is
Specific surface: 283m
2/ g
Bulk density: 0.54Kg/L
Intensity: 98N/cm
3000Nm in certain Steel Plant
3The work Sulfur capacity that/h coke oven gas desulfurization is is 67%.
Embodiment 2:
The production and the applicable cases of certain natural gas conditioning factory sweetening agent:
Produce the sweetening agent raw material: the sedimentary ironic hydroxide 56% of ferrous sulfate, methyl alcohol 3%, tar 1.6%, lime and 425 cement 8%, all the other are stopping composition.
Mediating 30 minutes kneading time after the above raw material mixing.
After the kneading, material is shaped to the strip of Φ 4mm through extrusion or other method, 30～50 ℃ low-temperature zone constant temperature 2 hours, is warmed up to the middle-temperature section constant temperature 0.6 hour about 80 ℃ again, finishes drying at 200 ℃ at last.
Through test, the crucial physical and chemical index of this sweetening agent is
Specific surface: 174m
2/ g
Bulk density: 0.48Kg/L
Intensity: 123N/cm
8000Nm in selexol process factory
3The work Sulfur capacity of/h selexol process is 36%.
Claims (5)
1 the invention provides the sweetening agent production method of a kind of high reactivity, high Sulfur capacity and high abrasion resistance strength, it is characterized in that:
1.1 add ethanol (alcohol or wine), acetic acid (vinegar), naphthalene, tar, kerosene, vegetables oil or the like volatility and hydrophobic nature pore-forming material in the sweetening agent raw material that needs are mediated, additional proportion is 0.01% to 35%, fully mediates then.
1.2 add solidifying agent such as water glass, cement, lime, Starso simultaneously in the sweetening agent raw material that needs are mediated, additional proportion is 0.01% to 15%, fully mediates then.
1.3 the sweetening agent drying means after extrusion or other method moulding is to adopt at normal temperatures to dry, if in baking oven, dry, then need to adopt temperature-programmed mode, temperature programming is at 30～50 ℃ low-temperature zone constant temperature more than 3 hours, be warmed up to middle-temperature section constant temperature about 80 ℃ again more than 0.5 hour, finish drying below 200 ℃ at last.
2 is according to claim 1, it is characterized in that the volatility pore-forming material will volatilize at normal temperatures easily in 1.1 to be gas, and sweetening agent is formed the pore-creating effect, can add wherein a kind of, also can add wherein multiple.
3 is according to claim 1, it is characterized in that in 1.1 the hydrophobic nature pore-forming material to have concurrently the volatility pore-forming material at normal temperatures easily volatilization be the function of gas, simultaneously to sweetening agent formation pore-creating effect, can add wherein a kind of, also can add wherein multiple.
4 is according to claim 1, it is characterized in that volatility pore-forming material and hydrophobic nature pore-forming material can add simultaneously in 1.1.
5 methods according to claim 1 is characterized in that solidifying agent water glass, cement, lime, the Starso in 1.2 can add simultaneously, also can add wherein one or both.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 200510022065 CN1966625A (en) | 2005-11-14 | 2005-11-14 | Normal temperature high activity high-sulfur accommodation high-strength desulfurizer production method |
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|---|---|---|---|
| CN 200510022065 CN1966625A (en) | 2005-11-14 | 2005-11-14 | Normal temperature high activity high-sulfur accommodation high-strength desulfurizer production method |
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| CN1966625A true CN1966625A (en) | 2007-05-23 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102335546A (en) * | 2010-07-28 | 2012-02-01 | 中国石油化工股份有限公司 | Preparation method of normal temperature iron oxide desulfurizing agent |
| CN103301873A (en) * | 2012-03-09 | 2013-09-18 | 中国石油天然气股份有限公司 | Preparation method for catalytic cracking catalyst |
| CN103341317A (en) * | 2013-07-24 | 2013-10-09 | 广州博能能源科技有限公司 | Deodorant and preparation method and application thereof |
| CN109092311A (en) * | 2017-06-21 | 2018-12-28 | 神华集团有限责任公司 | Low-temp desulfurization catalyst and the method that low-temp desulfurization catalyst is prepared by Fischer-Tropsch synthetic iron-based catalyst waste material |
-
2005
- 2005-11-14 CN CN 200510022065 patent/CN1966625A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102335546A (en) * | 2010-07-28 | 2012-02-01 | 中国石油化工股份有限公司 | Preparation method of normal temperature iron oxide desulfurizing agent |
| CN103301873A (en) * | 2012-03-09 | 2013-09-18 | 中国石油天然气股份有限公司 | Preparation method for catalytic cracking catalyst |
| CN103301873B (en) * | 2012-03-09 | 2016-02-10 | 中国石油天然气股份有限公司 | The preparation method of catalytic cracking catalyst |
| CN103341317A (en) * | 2013-07-24 | 2013-10-09 | 广州博能能源科技有限公司 | Deodorant and preparation method and application thereof |
| CN103341317B (en) * | 2013-07-24 | 2015-08-26 | 广州博能能源科技有限公司 | Deodorant and its preparation method and application |
| CN109092311A (en) * | 2017-06-21 | 2018-12-28 | 神华集团有限责任公司 | Low-temp desulfurization catalyst and the method that low-temp desulfurization catalyst is prepared by Fischer-Tropsch synthetic iron-based catalyst waste material |
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Open date: 20070523 |