CN1085103C - Desulfurizer for refining gas and its preparation method - Google Patents
Desulfurizer for refining gas and its preparation method Download PDFInfo
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Abstract
一种气体精制用脱硫剂及其制备方法。现有的脱硫剂一般只能脱除硫化氢，而不能同时脱除气体中存在的其他有机硫化物，而且其容硫的能力也较低。为了解决上述问题，本发明脱硫剂以活性炭为载体，担载一定量的过渡金属和有机胺，使本发明的脱硫剂在脱除硫化氢的同时，也能有效脱除有机硫。更为突出的是使其硫容量大幅度提高。A gas refining desulfurizer and a preparation method thereof. Existing desulfurizers generally can only remove hydrogen sulfide, but cannot remove other organic sulfides present in the gas at the same time, and their ability to accommodate sulfur is also low. In order to solve the above problems, the desulfurization agent of the present invention uses activated carbon as a carrier to support a certain amount of transition metals and organic amines, so that the desulfurization agent of the present invention can effectively remove organic sulfur while removing hydrogen sulfide. What is more prominent is that its sulfur capacity is greatly improved.
Description
The present invention relates to the desulfurizing agent that a kind of normal temperature removes hydrogen sulfide and organic sulfur.
The alternate absorption of gas-solid is a kind of important approach of the desulfuration purification of petrochemical materials gas and product gas.The acid water that devices such as oil plant atmospheric and vacuum distillation, catalytic cracking, hydrocracking and hydrofinishing produce can purify with stripping process, and reclaims sulphur and ammonia.Obtain liquefied ammonia after the refining compression of the rich ammonia vapour that stripping goes out.But, remove in the ammonia after the crystallisation adsorption and contain excessive H because the sour crude amount that refine present each refinery greatly increases
2Outside the S, also contain low boiling organic sulfurs such as first, ethyl sulfide, first, ethyl mercaptan, carbon disulfide.In order to guarantee liquid ammonia quality, require H in the liquefied ammonia
2S content will be lower than 5 μ g/g (being preferably lower than 1 μ g/g), and organic sulfur content is lower than 0.1 μ g/g.
Activated carbon desulphurization agent and the ZnO desulfurizing agent of mentioning Kunshan fine chemistry industry research institute in " application in the thick ammonia refining desulfurization of sour water stripping technology of KC-2 and KT310 desulfurizing agent " literary composition of " petroleum refining and chemical industry " the 27th volume the 10th phase (1996) are applied in the ammonia of some oil plants is refining.Before activated carbon desulphurization agent is arranged on ammonia compressor, be that extraordinary high grade activated carbon soaks metal through modification and forms.After the ZnO desulfurizing agent is arranged on ammonia compressor, need establish except that the lubricating oil facility, pipeline and equipment need insulation, have increased investment.A kind of low concentration H that removes has been proposed among the Chinese patent CN1105174A
2The oxidized form desulfurizing agent of S will use down at 60-180 ℃, but can not transform organic sulfur.Proposed a kind of catalyst that passes through the gas of claus reaction or hydrolysis processing sulfur-containing compound among the Chinese patent CN1123713A, but needed to use down at 320 ℃.More than two kinds of methods all exist reaction temperature too high, can not effectively remove H simultaneously
2Problem such as S and organic sulfur.Proposed a kind of normal temperature transformant desulfurizing agent among the Chinese patent CN1095963A, can transform absorption H down at 20-40 ℃
2S, COS, CS
2, but not good to the removal effect of mercaptan, thioether, and H
2S, COS, CS
2Adsorption capacity low.
The objective of the invention is to solve the deficiency of conventional art, provide a kind of can the conversion simultaneously to absorb H
2S, CH
3SH, CH
3SCH
3, CS
2, COS desulfurizing agent, and at normal temperatures and pressures separately use can reach the purpose of smart desulfurization, and improve H
2S, CH
3SH, CH
3SCH
3, CS
2, COS transforms absorptive capacity.
Desulfurizing agent of the present invention is a carrier with cylindricality or spherical activated charcoal, adopt to divide soak or altogether the method for soaking add one or more soluble compounds that are selected from transition metal V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ag, W (water soluble or ethanol, acetone), a kind of hydroxide or salt and a kind of organic amine that is selected from ethylenediamine, butanediamine, di-iso-butylmanice, hexamethylene diamine, diethanol amine, diphenylamine etc. that is selected from alkali and alkaline-earth metal K, Ca, Na, Mg.The addition of transition metal is counted the 0.2-8% of vehicle weight with weight metal, and alkali and alkaline-earth metal addition are counted the 0-15% of vehicle weight with metal oxide weight, and the addition of organic amine is the 1-25% of vehicle weight.The BET specific area of desulfurizing agent of the present invention is 1000m
2/ g, the pore volume of measuring with the mercury osmosis is 150-600cm
3/ rise desulfurizing agent.
Desulfurizing agent of the present invention prepares by following method.Be active carbon and vanadic sulfate, H
2WO
4, NiCl
2, H
3PO
3(MoO
3)
4, Fe
2Cl
3Deng in one or more soluble transition metal compounds, one or more organic amine branches that reach in ethylenediamine, butanediamine, di-iso-butylmanice, hexamethylene diamine, diethanol amine, the diphenylamines soaked or soak altogether 6-24 hour, in 70-120 ℃ stove dry 14～20 hours, again in nitrogen at 250～350 ℃ of following roasting 1-3 hours.
Can also support one or more alkali metal or alkaline earth metal compound in the desulfurizing agent of the present invention.Alkali metal compound wherein can be selected from KAC, NaAC, HCOOK, HCOONa, K
2CO
3, KHCO
3, Na
2CO
3, NaHCO
3, among NaOH, the KOH etc. one or more.
The carrier that desulfurizing agent of the present invention adopts is an active carbon.Activated carbon surface is the apolar surfaces of hydrophobic oleophylic.As stated above the surface of Zhi Bei desulfurizing agent have many by transition metal and (or) the organic metal activated centre that is combined into of alkaline-earth metal and organic amine.This activated centre has difunctional, to H
2The oxidation of S and the hydrolysis of organic sulfur all have catalytic activity.Organic amine group wherein is to the H in the gas phase
2S has certain sucking action, to transition metal-catalyzed H
2The S oxidation is favourable; And the existence of transition metal has reduced the hydrophobicity of activated carbon surface, and is favourable to organic amine group catalysis tempreture organic sulphur hydrolysis.Therefore, two kinds of functions in this activated centre are mutually promoted, and make desulfurizing agent of the present invention to H
2S and organic sulfur all have higher adsorption capacity.
Desulfurizing agent of the present invention is to utilize H under the normal temperature
2The chemisorption on the oxidation of S and the hydrolysis of organic sulfur and desulfurizing agent surface is realized the purification to sulfurous gas.Be used for H in the gas
2The gas that contains free oxygen that S is oxidized into sulphur generally is air (also can adopt pure oxygen, oxygen-enriched air).With before desulfurizing agent contacts, the gas that Ying Xianyu contains free oxygen mixes, and makes O in the gaseous mixture at pending gas
2: H
2The mol ratio of S is 0.5-3, particularly 0.5-1.5.The minor amount of water that participates in tempreture organic sulphur hydrolysis does not need to add in addition, and the Trace Water Vapor that contains in the general gas is just enough.
Desulfurizing agent of the present invention is used for handling the H of petrochemical materials gas and product gas
2S and organic sulfur are as H wherein
2S≤400 μ g/g, total organic sulfur (CH
3SH+CH
3SCH
3+ COS+C
2S)≤120 during μ g/g, pending gas is with after desulfurizing agent contacts at normal temperatures and pressures, H
2S concentration can be reduced to below the 5 μ g/g, total organic sulfur (CH
3SH+CH
3SCH
3+ COS+C
2S)≤0.1 μ g/g.Characteristics such as adopt desulfurizing agent of the present invention that petrochemical materials gas and product gas are carried out desulfuration purification, have the Sulfur capacity height, flow process is simple, and stable operation is convenient, and treatment effect is good are specially adapted to the desulfuration purification of oil plant acid water stripping ammonia.
Composition, preparation and the effect of this desulfurizing agent are described below by embodiment.
Carry out the evaluation of desulfurizing agent on micro device (10ml), the ratio of height to diameter of bed is 3: 1.Pending gas contacts with desulfurizing agent under 0-0.08MPa, 25 ℃ of constant temperature, and STP time of contact is 3 seconds.The concentration of sulfur component is as follows in the pending gas: H
2S 100 μ g/g; CH
3SH 20 μ g/g; CH
3SCH
320 μ g/g; CS
220 μ g/g; COS 20 μ g/g.In addition, O in the pending gas
2Content is about 80 μ g/g.Leave the sulfur content of each form in the gas of reactor with gas chromatographic analysis.The Sulfur capacity of desulfurizing agent is with the H of absorption
2S and organic sulfur weight account for the percentage meter (wt%) of vehicle weight.
Embodiment 1
With 260 weight parts waters, x weight portion (x=1,5,8,12,15,20) NiCl
2The aqueous solution of making floods the active carbon of 100 weight portions, evaporate the moisture of gained mixture then with rotary evaporator, drying is 12 hours in 100 ℃ stove, again in nitrogen after 300 ℃ of following roastings 3 hours, the aqueous solution made from 100 weight parts waters and 5 weight portion butanediamine floods the first step product 12 hours of 100 weight portions under 40 ℃ of constant temperature, evaporate the moisture of gained mixture then with rotary evaporator, drying is 12 hours in 80 ℃ stove, again in nitrogen 300 ℃ of following roastings 1 hour, obtain desulfurizing agent A, B, C, D, E and F.The content of its nickel metal is respectively 0.4wt%, 2.4wt%, 3.8wt%, 5.7wt%, 7.2wt% and 9.6wt%.
The Sulfur capacity of desulfurizing agent A, B, C, D, E and F sees the following form:
The Sulfur capacity of table 1 desulfurizing agent A-F
| Desulfurizing agent | Sulfur capacity, wt% | ||||
| H 2S | CH 3SH | CH 3SCH 3 | CS 2 | COS | |
| A | 19.6 | 5.7 | 4.6 | 2.4 | 6.0 |
| B | 22.4 | 5.3 | 4.8 | 2.3 | 5.8 |
| C | 20.5 | 5.7 | 4.4 | 2.5 | 6.4 |
| D | 20.3 | 5.8 | 4.9 | 2.4 | 6.2 |
| E | 16.4 | 5.6 | 5.0 | 2.6 | 6.4 |
| F | 12.3 | 5.4 | 4.8 | 2.3 | 6.3 |
As seen from the above table, desulfurizing agent of the present invention all has higher adsorption capacity to various sulfur-containing compounds.
Embodiment 2
With 260 weight parts waters, 5 weight portion NiCl
2The aqueous solution of making floods the active carbon of 100 weight portions, evaporate the moisture of gained mixture then with rotary evaporator, drying is 12 hours in 100 ℃ stove, again in nitrogen after 300 ℃ of following roastings 3 hours, use 100 weight parts waters, x weight portion KAC (x=1,5,8,10,14 and 20) and the aqueous solution made of 5 weight portion butanediamine under 40 ℃ of constant temperature, flood the first step product 12 hours of 100 weight portions, evaporate the moisture of gained mixture then with rotary evaporator, in 80 ℃ stove dry 12 hours, again in nitrogen 300 ℃ of following roastings 1 hour, obtain desulfurizing agent G, H, I, J, K and L.The content of its KAC is respectively 1wt%, 5wt%, 8wt%, 10wt%, 14wt% and 20wt%.
The Sulfur capacity of desulfurizing agent G, H, I, J, K and L sees the following form:
The Sulfur capacity of table 2 desulfurizing agent G-L
| Desulfurizing agent | Sulfur capacity, wt% | ||||
| H 2S | CH 3SH | CH 3SCH 3 | CS 2 | COS | |
| G | 23.0 | 4.9 | 4.4 | 1.9 | 5.6 |
| H | 24.4 | 5.2 | 4.6 | 2.2 | 5.8 |
| I | 25.0 | 5.5 | 4.9 | 2.3 | 6.2 |
| J | 23.3 | 5.4 | 5.0 | 2.1 | 6.1 |
| K | 23.8 | 5.2 | 4.7 | 2.0 | 6.0 |
| L | 22.3 | 4.7 | 4.5 | 1.9 | 5.8 |
As seen from the above table, add alkali metal compound and can further improve desulfurizing agent of the present invention H
2The adsorption capacity of S.
Embodiment 3
With 260 weight parts waters, 5 weight portion NiCl
2The aqueous solution of making floods the active carbon of 100 weight portions, evaporate the moisture of gained mixture then with rotary evaporator, drying is 12 hours in 100 ℃ stove, again in nitrogen after 300 ℃ of following roastings 3 hours, use 100 weight parts waters, 5 weight portion KAC and x weight portion butanediamine (x=1,4,8,10,14 and 18) aqueous solution of making floods the first step product 12 hours of 100 weight portions under 40 ℃ of constant temperature, evaporates the moisture of gained mixture then with rotary evaporator, in 80 ℃ stove dry 12 hours, again in nitrogen 300 ℃ of following roastings 1 hour, obtain desulfurizing agent M, N, O, P, Q and R.The content of its butanediamine is respectively 1wt%, 4wt%, 8wt%, 10wt%, 14wt% and 18wt%.
The Sulfur capacity of desulfurizing agent M, N, O, P, Q and R sees the following form:
The Sulfur capacity of table 3 desulfurizing agent M-R
| Desulfurizing agent | Sulfur capacity, wt% | ||||
| H 2S | CH 3SH | CH 3SCH 3 | CS 2 | COS | |
| M | 23.5 | 5.0 | 4.8 | 2.2 | 5.9 |
| N | 22.9 | 5.2 | 4.9 | 2.3 | 6.2 |
| O | 24.0 | 5.4 | 4.8 | 2.3 | 6.1 |
| P | 24.2 | 5.3 | 4.7 | 2.0 | 5.9 |
| Q | 24.0 | 4.9 | 4.4 | 1.9 | 5.7 |
| R | 23.9 | 4.6 | 4.2 | 1.8 | 5.5 |
Embodiment 4
Press embodiment 1 described method, the aqueous solution made from 220 weight parts waters, 5 weight portion vanadic sulfates and 8 weight portion NaOH floods the active carbon of 100 weight portions; With 5 weight portion HCOOK, 5 weight portion di-iso-butylmanices dipping, obtain desulfurizing agent A ' again.
Desulfurizing agent A ' respectively 20,30,40,50,60 with 70 ℃ under (other conditions are constant) contact Sulfur capacity that records such as following table with pending gas:
The Sulfur capacity of table 4 desulfurizing agent A ' under different temperatures
| Temperature, ℃ | Sulfur capacity, wt% | ||||
| H 2S | CH 3SH | CH 3SCH 3 | CS 2 | COS | |
| 20 | 23.2 | 5.0 | 4.8 | 2.1 | 5.4 |
| 30 | 24.1 | 5.2 | 4.9 | 2.2 | 6.2 |
| 40 | 24.0 | 5.6 | 4.6 | 2.1 | 6.7 |
| 50 | 24.2 | 6.2 | 4.2 | 1.9 | 7.8 |
| 60 | 24.0 | 7.1 | 3.6 | 1.7 | 8.9 |
| 70 | 23.8 | 7.3 | 2.9 | 1.3 | 7.2 |
As can be seen from the table, variation of temperature is to H
2The Sulfur capacity influence of S is little, improves temperature to increasing CH
3The Sulfur capacity of SH and COS is favourable, and lower temperature is to improving CH
3SCH
3Favourable with the Sulfur capacity of COS.
Embodiment 5
Press embodiment 1 described method, with 200 weight parts waters, 10 weight portion H
2WO
4The aqueous solution made from 1 weight portion NaOH floods the active carbon of 100 weight portions again with 5 weight portion HCOONa, 5 weight portion diphenylamines dipping, obtains desulfurizing agent B '.
Desulfurizing agent B ' is at O
2When content is respectively 50,100,150,200,250 and 300 μ g/g (other conditions are constant), Sulfur capacity that records such as following table:
Table 5 desulfurizing agent B ' is at different O
2Sulfur capacity under the content
| O 2Concentration, μ g/g | Sulfur capacity, wt% | ||||
| H 2S | CH 3SH | CH 3SCH 3 | CS 2 | COS | |
| 50 | 24.6 | 5.0 | 5.0 | 1.9 | 6.2 |
| 100 | 25.4 | 5.2 | 4.9 | 2.2 | 5.8 |
| 150 | 25.0 | 5.1 | 4.7 | 2.3 | 4.8 |
| 200 | 23.8 | 5.0 | 4.2 | 2.1 | 4.8 |
| 250 | 21.8 | 4.9 | 4.1 | 2.0 | 4.6 |
| 300 | 18.9 | 4.6 | 4.1 | 1.9 | 4.3 |
As seen from the above table, O
2Concentration is preferably in 50-150 μ g/g, i.e. O
2: H
2The mol ratio of S is 0.5-1.5.
Embodiment 6
Press embodiment 1 described method, with 150 weight parts waters, 10 weight portion phosphomolybdic acid H
3PO
3(MoO
3)
4The aqueous solution made from 0.5 weight portion NaOH floods the active carbon of 100 weight portions, with 5 weight portion NaAC, 5 weight portion diethanol amine dipping, obtains desulfurizing agent C ' again.
Under aforesaid experimental condition, desulfurizing agent C ' was at 30 days continuous cycle of operation inner outlet H
2S does not detect all the time, total organic sulfur (CH
3SH+CH
3SCH
3+ CS
2+ COS)≤0.1 μ g/g.
Embodiment 7
Press embodiment 1 described method, with the FeCl of 100 weight parts waters, 6 weight portions
3Flood the active carbon of 100 weight portions, again with 5 weight portion NaHCO
3, 5 weight portion hexamethylene diamines dippings, obtain desulfurizing agent D '.
Under aforesaid experimental condition, desulfurizing agent D ' was at 30 days continuous cycle of operation inner outlet H
2S does not detect all the time, total organic sulfur (CH
3SH+CH
3SCH
3+ CS
2+ COS)≤0.1 μ g/g.
Embodiment 8
Press embodiment 1 described method, with the AgNO of 200 weight parts waters, 5 weight portions
3Flood the active carbon of 100 weight portions, again with 5 weight portion KHCO
3, 5 weight portion diphenylamines dippings, obtain desulfurizing agent E '.
Under aforesaid experimental condition, desulfurizing agent E ' was at 30 days continuous cycle of operation inner outlet H
2S does not detect all the time, total organic sulfur (CH
3SH+CH
3SCH
3+ CS
2+ COS)≤0.1 μ g/g.
Claims (6)
1, a kind of refining desulfurizing agent of sulfurous gas that is used for, with the active carbon is carrier, support the soluble compound that one or more are selected from transition metal V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Mo, Ag, W, it is characterized in that also supporting the organic amine that one or more are selected from ethylenediamine, butanediamine, di-iso-butylmanice, hexamethylene diamine, diethanol amine, diphenylamines, and one or more are selected from the compound of alkalies and alkaline earth, and its composition is counted with vehicle weight:
Transition metal weight metal meter 0.20～8.00%;
Organic amine organic amine weight meter 1.00～25.00%;
Alkalies and alkaline earth is by metal oxide 0.00～15.00%.
2,, it is characterized in that supporting the organic amine of the alkali of transition metal in vehicle weight 0.20～7.00%, 5.00～10.00wt% and alkaline-earth metal, 2.00～10.00wt% according to the desulfurizing agent of claim 1.
3,, it is characterized in that the specific area 1000m of carrier active carbon according to the desulfurizing agent of claim 1
2/ g, pore volume are 150～600cm
3/ rise desulfurizing agent.
4, the preparation method of the described desulfurizing agent of a kind of claim 1, the adding employing that it is characterized in that active material divides the method for soaking or soaking altogether, dip time is 6～24 hours, and in 70～120 ℃ stove dry 14～20 hours, again in nitrogen 250～350 ℃ of following roastings 1～3 hour.
5, the application of the described desulfurizing agent of a kind of claim 1 is characterized in that this desulfurizing agent is used for H
2S≤400 μ g/g, total organic sulfur (CH
3SH+CH
3SCH
3+ COS+C
2S)≤120 the desulfuration purification of the petrochemical materials gas of μ g/g and product gas.
6,, it is characterized in that this desulfurizing agent is used for the desulfuration purification of oil plant acid water ammonia that stripping produces according to the described application of claim 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114464A CN1085103C (en) | 1998-11-13 | 1998-11-13 | Desulfurizer for refining gas and its preparation method |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN98114464A CN1085103C (en) | 1998-11-13 | 1998-11-13 | Desulfurizer for refining gas and its preparation method |
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|---|---|
| CN1253847A CN1253847A (en) | 2000-05-24 |
| CN1085103C true CN1085103C (en) | 2002-05-22 |
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|---|---|---|---|
| CN98114464A Expired - Fee Related CN1085103C (en) | 1998-11-13 | 1998-11-13 | Desulfurizer for refining gas and its preparation method |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331567C (en) * | 2003-03-18 | 2007-08-15 | 于文波 | Sulfur dioxide removing agent |
| CN100344378C (en) * | 2005-11-30 | 2007-10-24 | 曹志德 | Desulfur denitrogen catalyst of fuel coal, fuel oil boiler smoke and its desulfur denitrogen method |
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|---|---|---|---|---|
| CN1095963A (en) * | 1994-03-12 | 1994-12-07 | 湖北省化学研究所 | Auto-vulcanization hydrogen, sulphur carbonoxide, carbon disulfide inversion absorption type desulfurizing agent and preparation |
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- 1998-11-13 CN CN98114464A patent/CN1085103C/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095963A (en) * | 1994-03-12 | 1994-12-07 | 湖北省化学研究所 | Auto-vulcanization hydrogen, sulphur carbonoxide, carbon disulfide inversion absorption type desulfurizing agent and preparation |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1331567C (en) * | 2003-03-18 | 2007-08-15 | 于文波 | Sulfur dioxide removing agent |
| CN100344378C (en) * | 2005-11-30 | 2007-10-24 | 曹志德 | Desulfur denitrogen catalyst of fuel coal, fuel oil boiler smoke and its desulfur denitrogen method |
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|---|---|
| CN1253847A (en) | 2000-05-24 |
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