CN100375651C - Multicomponent composite desulfate catalyst - Google Patents
Multicomponent composite desulfate catalyst Download PDFInfo
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- CN100375651C CN100375651C CNB2005100188632A CN200510018863A CN100375651C CN 100375651 C CN100375651 C CN 100375651C CN B2005100188632 A CNB2005100188632 A CN B2005100188632A CN 200510018863 A CN200510018863 A CN 200510018863A CN 100375651 C CN100375651 C CN 100375651C
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- phthalocyanine cobalt
- molysite
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Abstract
The present invention relates to polybasic composite desulphurization catalyst. The present invention is characterized in that the catalyst mainly contains the following components of cobalt phthalocyanine derivative, polyphenol class compound, molysite, ligand which can form a complex compound with the molysite, and a vanadium class compound, the contents of each component has the weight percent of 20% to 70% of cobalt phthalocyanine derivative, 10% to 50% of polyphenol class compound, 10% to 60% of molysite, 10% to 50% of ligand and 1% to 40% of vanadium class compound. The present invention has superior combination property, and reaches 98% of percentage of desulfurization for raw gas containing 5 to 10% of sulfur.
Description
Technical field
The present invention relates to a kind of wet oxidation process desulphurization catalyst, be specifically related to a kind of polynary hybrid system desulphurization catalyst.This desulphurization catalyst is mainly used in the ammonia synthesizing industry semiwater gas, and the desulfuration and decyanation of conversion gas also can be used for town gas, oven gas, and natural gas, synthesis gas, cracking gas and gasoline, sulphide-containing waste waters etc. need remove inorganic sulfur, the industry of organic sulfur.
Background technology
With coal, natural gas, oil gas, oil and products thereof is in the chiral process of raw material, sulphur in the raw material all will be converted into sulfide (hydrogen sulfide, sulphur carbonoxide, carbon disulfide, mercaptan, thioether, sulphur are luxuriant etc.), organic nitrogen compound will change into hydrogen cyanide, and their existence has a strong impact on chiral process---make catalyst poisoning and can't operation, etching apparatus, influence product quality and contaminated environment.Therefore just to become with coal, natural gas, oil gas, oil and products thereof be the necessary unit operations of chemical process industry (CPI) of raw material in desulfurization.
In the prior art, the method that removes sulfide is a lot, such as the active carbon in the dry method, iron oxide etc., ADA method, mimosa extract method, MSQ method, PDS method or the like in the wet method.Above-mentioned the whole bag of tricks and desulphurization catalyst respectively have advantage, but all there are some defectives in what, the Sulfur capacity that has in these methods is little, desulfuration efficiency is low, the stable operation for a long time that has, the operating cost height that has, the regeneration that has in use also produces secondary pollution because of difficulty, and it is not high to the more and more higher high sulfur removal rate that contains in the raw material also having a common shortcoming.
Phthalocyanine cobalt sulfonate class catalyst is as a kind of desulphurization catalyst of function admirable, be widely used in the desulfurization of various industrial gas from the 1980s, people constantly release follow-on cobalt phthalocyanine desulfating catalyst afterwards, and its desulfurization degree is not high to overcome, the shortcoming of fluctuation of service.In these follow-on cobalt phthalocyanine desulfating catalysts, the catalyst that with the patent No. is CN96119502 is more successful, it is in conventional (sulfur content restrains below every cubic metre 1.5 in the gas) sweetening process, desulfurization degree can reach 99%, but in high-sulfur more and more higher in the modern industry gas (sulfur content restrains more than every cubic metre 5 in the gas) system, its desulfurization degree only has about 90%, can not satisfy the desulfurization requirement of high-sulfur industry gas.
Summary of the invention
The purpose of this invention is to provide a kind of multicomponent composite desulfate catalyst, its combination property is superior, can effectively remove sulfide in the high Sulfur Contained Raw Gas, is practical efficient and environment-friendly type desulphurization catalyst.
For achieving the above object, the technical solution used in the present invention is: a kind of multicomponent composite desulfate catalyst is characterized in that mainly comprising following component:
(1) phthalocyanine cobalt derivative, this derivative are phthalocyanine cobalt sulfonate or poly phthalocyanine cobalt sulfonate or poly phthalocyanine cobalt first
Hydrochlorate;
(2) polyphenol compound: this polyphenol compound is a hydroquinones, resorcinol, catechol, phloroglucin, pyrogallol, the composition of one or more in the tannin;
(3) molysite, this molysite are thiocyanation iron or ferric carbonate;
(4) can form the ligand of complex compound with molysite;
(5) vanadium compounds, this vanadium compounds are vanadic anhydride or metavanadate; The percentage by weight of each constituent content is:
Phthalocyanine cobalt derivative 20%-50%
Polyphenol compound 10%-50%
Molysite 10%-15%
Ligand 10%-50%
Vanadium compounds 1%-40%.
Aforesaid multicomponent composite desulfate catalyst is characterized in that described:
(1) phthalocyanine cobalt sulfonate or poly phthalocyanine cobalt sulfonate or poly phthalocyanine cobalt formates are potassium or sodium or ammonium salt;
(4) can form the ligand of complex compound with molysite, this ligand is a citric acid, amino acid, tartaric acid, salicylic acid, the composition of one or more in the sulfosalicylic acid.
Aforesaid multicomponent composite desulfate catalyst is characterized in that: described catalyst is with the cushioning liquid of alkaline solution as catalyst.
Aforesaid multicomponent composite desulfate catalyst is characterized in that: the pH value of the doctor solution that described catalyst was made into is in the 7-11 scope.
Aforesaid multicomponent composite desulfate catalyst is characterized in that the alkaline matter of described alkaline solution is: the carbonate of ammoniacal liquor, ammonium, the bicarbonate of ammonium, alkali carbonate or alkali metal hydrogencarbonate.
The purposes of aforesaid multicomponent composite desulfate catalyst is characterized in that: be used for removing the industry of inorganic sulfur or organic sulfur with its doctor solution of preparing, as semiwater gas, town gas, oven gas, natural gas, synthesis gas, cracking gas and gasoline, sulphide-containing waste water etc.
Related content and change interpretation are as follows in the technique scheme:
The process of catalytic wet sulfur method is broadly divided into absorption, oxidation and three steps of regeneration, and the TM desulphurization catalyst is respectively described below in the effect in these three steps:
One. absorb
The main effect in this step is that the sulfide in the unstripped gas (as hydrogen sulfide etc.) is transferred in the doctor solution.When the doctor solution of liquid phase is contacted in desulfurizing tower with the unstripped gas of gas phase, sulfide in gas phase is absorbed by the doctor solution of alkalescence, reach the purpose that removes sulfide in the gas phase, this step is the key step of catalytic wet doctor treatment, the size of unstripped gas desulfurization degree, the height of purifying rate all are subjected to the control in this step, and its main chemical reactions is as follows:
H
2S(g)+Na
2CO
3(l)＝NaHS(l)+NaHCO
3(l)
Under certain temperature, basicity, the content of NaHS has determined the degree that this reaction is carried out in the doctor solution.Principle according to chemical balance, the content of NaHS is low more, helps above-mentioned reaction forward more and carries out, and just helps the absorption of doctor solution to the hydrogen sulfide of gas phase more, desulfurization degree is also just high more, otherwise high desulfurization rate is also just low more more as NaHS content in the doctor solution.As seen can the content of NaHS be one of crucial element that have high desulfurization degree in the doctor solution.The content of NaHS is controlled by next step mainly in the doctor solution.
Two. oxidation
This step is NaHS in the doctor solution will be oxidized to elemental sulfur fast in the presence of catalyst, to reach from doctor solution NaHS is removed out, the purpose of regenerative sulfur binding liquid.Its main chemical reactions is as follows:
The speed of this step reaction speed directly influences the equilibrium concentration of NaHS in the doctor solution.The main difference of different desulphurization catalyst systems is just on different to the performance of oxidation reaction catalysis.The product that catalytic activity is high can make oxidation reaction finish fast, makes the content of NaHS in the doctor solution very low, the balance that helps absorption reaction is cleaned hydrogen sulfide residual volume attenuating in the gas phase, and desulfurization degree rises, otherwise activity of such catalysts is low, and desulfurization degree descends.Phthalocyanine cobalt derivatives catalysis function admirable, using in industrial qi exhaustion sulphur has had for a long time, but this body structure of phthalocyanine cobalt derivative is a macromolecular compound, and polymerization easily, its mass transfer velocity is restricted, influenced the performance of its catalytic performance, feasible not high with the desulfurization degree of pure phthalocyanine cobalt derivative desulphurization system, can not satisfy the requirement of the high sulfur removal rate of modern industry gas.
Desulphurization catalyst of the present invention is at these characteristics of phthalocyanine cobalt derivative, in catalyst, introduced component---the molysite of micromolecular catalyst component and the polymerization of prevention phthalocyanine cobalt derivative, increased the mass transfer velocity of catalyst on the one hand, made full use of the valid density of phthalocyanine cobalt derivative on the other hand, make that the concentration of balance NaHS is very low in the doctor solution, absorption reaction is more complete, more thorough.Can improve the desulfurization degree that is cleaned gas greatly.
Three. the regeneration flotation
There are two effects in this step, the one, in regeneration tank, make catalyst return oxidation state from going back ortho states by the air that adds, another effect is to change matter sulphur into multi-joint sulphur by the air that adds, and flotates from doctor solution, to reach the purpose that sulphur is separated from doctor solution.Added component---the vanadium compounds that can promote to generate multi-joint sulphur in the desulphurization catalyst of the present invention, made the segregative multi-joint sulphur of the easier generation of elemental sulfur of generation.
The specific embodiment
Embodiment one, a kind of multicomponent composite desulfate catalyst, and the percentage by weight of its component and content is:
Phthalocyanine cobalt sodium sulfonate 50%
Hydroquinones 15%
Hexacyanoferrate sodium 15%
Gluconic acid sodium salt 10%
Sodium metavanadate 10%.
Above-mentioned desulphurization catalyst and sodium carbonate are made into alkaline solution, and the amount that wherein contains phthalocyanine cobalt sodium sulfonate is every cubic metre of a 5-6 gram, and the pH value of solution is 8-10, and when hydrogen sulfide content in the gas restrains every standard cubic meter when following 10, desulfuration efficiency can reach 98-99%.
Embodiment two, a kind of multicomponent composite desulfate catalyst, and the percentage by weight of its component and content is:
Phthalocyanine cobalt sodium formate 50%
Tannin extract 15%
Ferric carbonate 15%
Natrium citricum 10%
Vanadic anhydride 10%
Usage is with embodiment one.
Claims (5)
1. multicomponent composite desulfate catalyst is characterized in that mainly comprising following component:
(1) phthalocyanine cobalt derivative, this derivative are phthalocyanine cobalt sulfonate or poly phthalocyanine cobalt sulfonate or poly phthalocyanine cobalt formates;
(2) polyphenol compound; This polyphenol compound is a hydroquinones, resorcinol, catechol, phloroglucin, pyrogallol, the material of more than one in the tannin;
(3) molysite, this molysite are thiocyanation iron or ferric carbonate;
(4) can form the ligand of complex compound with molysite;
(5) vanadium compounds, this vanadium compounds are vanadic anhydride or metavanadate;
The percentage by weight of each constituent content is:
Phthalocyanine cobalt derivative 20%-50%
Polyphenol compound 10%-50%
Molysite 10%-15%
Ligand 10%-50%
Vanadium compounds 1%-40%.
2. multicomponent composite desulfate catalyst according to claim 1 is characterized in that described:
(1) phthalocyanine cobalt sulfonate or poly phthalocyanine cobalt sulfonate or poly phthalocyanine cobalt formates are potassium, sodium or ammonium salt;
(4) can form the ligand of complex compound with molysite, this ligand is a citric acid, amino acid, tartaric acid, salicylic acid, the material of more than one in the sulfosalicylic acid.
3. multicomponent composite desulfate catalyst according to claim 1 is characterized in that: described catalyst is with the cushioning liquid of alkaline solution as catalyst.
4. multicomponent composite desulfate catalyst according to claim 3 is characterized in that: the pH value of the doctor solution that described catalyst was made into is in the 7-11 scope.
5. multicomponent composite desulfate catalyst according to claim 3 is characterized in that the alkaline matter of described alkaline solution is: the carbonate of ammoniacal liquor, ammonium, the bicarbonate of ammonium, alkali carbonate or alkali metal hydrogencarbonate.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100188632A CN100375651C (en) | 2005-06-07 | 2005-06-07 | Multicomponent composite desulfate catalyst |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100188632A CN100375651C (en) | 2005-06-07 | 2005-06-07 | Multicomponent composite desulfate catalyst |
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| CN1724162A CN1724162A (en) | 2006-01-25 |
| CN100375651C true CN100375651C (en) | 2008-03-19 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103937577B (en) * | 2014-03-17 | 2016-03-30 | 中国地质大学（北京） | A kind of modified Bayer process red mud-mineral material works in coordination with coal-fired sulfur fixing agent |
| CN103920388B (en) * | 2014-04-30 | 2016-04-20 | 福建三聚福大化肥催化剂国家工程研究中心有限公司 | A kind of Compound type desulfurization grout containing complexing agent and preparation method thereof |
| CN110628475B (en) * | 2018-06-21 | 2020-11-13 | 中国石油化工股份有限公司 | Process for pretreating rich gas in refinery and process for desulfurizing dry gas and/or liquefied gas |
| CN110628476B (en) * | 2018-06-21 | 2020-11-13 | 中国石油化工股份有限公司 | Pretreatment method and purifying agent for refinery rich gas and desulfurization method for dry gas and/or liquefied gas |
| CN109266402A (en) * | 2018-10-23 | 2019-01-25 | 唐钢美锦（唐山）煤化工有限公司 | A kind of do not stop production reduces the device and method of desulfurization pressure tower |
| CN112642287A (en) * | 2019-10-12 | 2021-04-13 | 中石化南京化工研究院有限公司 | Environment-friendly composite solvent for desulfurization by wet oxidation method |
| CN112642576B (en) * | 2020-09-17 | 2022-02-01 | 中南大学 | Selective oxidation and flotation separation method for pyrite gangue in sulfide ore |
| CN112138723A (en) * | 2020-10-23 | 2020-12-29 | 田作林 | Desulfurization catalyst and preparation method thereof |
| CN114904532A (en) * | 2022-06-06 | 2022-08-16 | 河南美源环保新材料有限公司 | Preparation method of desulfurization catalyst |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154998A (en) * | 1996-10-23 | 1997-07-23 | 冶金工业部鞍山焦化耐火材料设计研究院 | Ammonia coke-oven-gas desulfurization and decyanation technology by using hydrochinone phthalocyanine cobalt sulfonate as composite catalyst |
| CN1277245A (en) * | 2000-04-20 | 2000-12-20 | 江苏苏钢集团有限公司 | Coke-oven gas desulfurizing and decyanating process |
| US20030052044A1 (en) * | 2001-06-19 | 2003-03-20 | Greaney Mark A. | Naphtha desulfurization method |
-
2005
- 2005-06-07 CN CNB2005100188632A patent/CN100375651C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1154998A (en) * | 1996-10-23 | 1997-07-23 | 冶金工业部鞍山焦化耐火材料设计研究院 | Ammonia coke-oven-gas desulfurization and decyanation technology by using hydrochinone phthalocyanine cobalt sulfonate as composite catalyst |
| CN1277245A (en) * | 2000-04-20 | 2000-12-20 | 江苏苏钢集团有限公司 | Coke-oven gas desulfurizing and decyanating process |
| US20030052044A1 (en) * | 2001-06-19 | 2003-03-20 | Greaney Mark A. | Naphtha desulfurization method |
Non-Patent Citations (3)
| Title |
|---|
| MSQ－3高效脱硫新技术的研究开发. 庞捷等.河南科学，第21卷第(2)期. 2003 * |
| PDS脱硫脱氰催化剂的现状. 杨树卿.燃料与化工，第33卷第(6)期. 2002 * |
| 湿式氧化法脱硫的技术进展. 梁锋.现代化工，第23卷第(5)期. 2003 * |
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