CN101195778A - Production method of natural gas fine purification desulphurizing agent - Google Patents
Production method of natural gas fine purification desulphurizing agent Download PDFInfo
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- CN101195778A CN101195778A CNA2008100451227A CN200810045122A CN101195778A CN 101195778 A CN101195778 A CN 101195778A CN A2008100451227 A CNA2008100451227 A CN A2008100451227A CN 200810045122 A CN200810045122 A CN 200810045122A CN 101195778 A CN101195778 A CN 101195778A
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Abstract
The invention relates to a preparation method for natural gas refining desulphurizer in the natural gas processing field. Cyclodextrin molecules in the desulphurizer can effectively identify organic sulfur molecules in natural gas and are contained in a cyclodextrin cavity, and thereby the purpose of refining desulfuration is achieved. The invention adopts the technology proposals that AlCl3 and sodium hydroxide are dissolved in a certain amount of water according to mol ratio of 1 : 3, and Al(OH)3 sol is prepared; then silica sol and cyclodextrin are added into the Al(OH)3 sol, the mol ratio of Al(OH)3 to SiO2 to the cyclodextrin is 0.1 : 1 : 0.1 to 1, the stirring is performed at room temperature to prepare sol, the time of the stirring is 2 to 6 hours, and the rotating speed of the stirring is 1000 r/min; then the temperature is risen to 60 to 80 DEG C, and the stirring is continuously performed to react for 6 to 20 hours; after the reaction is finished, the temperature is risen to 90 to 130 DEG C to perform crystallization, and finally the desulphurizer is formed through cleaning, drying, and pressing. The desulphurizer prepared through the invention can effectively remove organic sulfur in the natural gas and simplify a refining desulfuration process, the refining desulfuration cost is reduced, and the invention can be widely used for the refining desulfuration of the natural gas.
Description
Technical field
The present invention relates to a kind of preparation method of natural gas fine purification desulphurizing agent, the sweetening agent of this method preparation can remove organosulfur in the Sweet natural gas effectively, can simplify refining desulfurization technology, reduce the refining desulfurization cost, belong to the preparation method of natural gas processing field chemical assistant.
Technical background
Contained sulfide substantially all is with H in the Sweet natural gas
2The form of S and organic sulfide exists, their sour gas that is otherwise known as, and the existence of these gases can cause metallic material corrosion, and contaminate environment.When Sweet natural gas during as industrial chemicals, they also can cause poisoning of catalyst, influence quality product.Therefore the purpose of selexol process is the specification that the above-mentioned impurity composition in the gas is removed to requirement by different purposes.With the Sweet natural gas synthesizing methanol is example, and the sulphur content that is used for the unstripped gas of synthesizing methanol requires at 1mg/m
3Below.Synthesize must when being raw material, before adopting steam reforming, just sulfide need be removed totally in the production so refining desulfurization is a methyl alcohol, do not make the nickel catalyzator poisoning to satisfy steam reforming process through step with the Sweet natural gas.The outsourcing Sweet natural gas of most of methanol device has all passed through the purifying treatment of natural gas companies, and sulphur content is not high, is 20mg/m
3About, contain a certain amount of organosulfur.Raw natural gas makes organosulfur be catalytically conveted to inorganic sulfur by cobalt molybdenum hydrogenation, through the smart desulfurization of zinc oxide, just can satisfy the requirement of nickel catalyzator again.This shows that the natural gas fine purification desulfurization is the technological process of a more complicated, and dry desulfurizing process is adopted in the smart desulfurization of Sweet natural gas more, most of dry-desulphurizer, the efficient of organic sulfide removal is not high, and going here and there in its front usually has the device of organosulfur hydrocracking and tempreture organic sulphur hydrolysis.Limited by organic sulfur capacity, the unstripped gas total sulfur content that advances dry desulfurization can not be too high, otherwise desulphurization cost increases.
Natural gas fine purification desulfurization main purpose is for organic sulfide removal, and these organosulfurs mainly comprise: mercaptan, thioether, dithiocarbonic anhydride and carbon oxysulfide.These sulfocompound molecules are except carbon containings all, and it all is hydrophobic also having a common feature and be exactly them.The present invention just is being based on that their this common feature proposes.
The present invention proposes to utilize cyclodextrin to make sweetening agent for raw material and removes organosulfur in the Sweet natural gas.(cyclodextrin is to act on the resulting one group of cyclic oligosaccharide of starch by cyclomaltodextrin glucanotransferase (CGTase) CD) to cyclodextrin.Find to contain the multiple cyclodextrin of six to 12 glucose units at present, modal have α-CD, β-CD, a γ-CD, they are connect with α-1,4 glycosidic link by 6,7 and 8 glucopyranose units respectively and form, and shape of molecule is slightly tapered annulus.α-CD internal diameter 0.48nm, external diameter 1.46nm, high 0.78nm, the chamber internal volume is about 0.17nm
3β-CD internal diameter 0.78nm, external diameter 1.53nm, high 0.78nm, the chamber internal volume is about 0.37nm
3γ-CD internal diameter 0.83nm, external diameter 1.75nm, high 0.78nm, the chamber internal volume is about 0.43nm
3C-3 in the Glucopyranose molecule, C-5 hydrogen atom and the inwall that becomes the Sauerstoffatom formation tube of glycosides make cavity inside become the hydrophobicity space, and 2,3,6 hydroxyls of glucosyl residue are positioned at the outside of barrel, possess hydrophilic property.The compound formation inclusion compound that hydrophobic, the outer hydrophilic special construction that removes addendum cone shape cavity can adapt to structure and character in it.Because the organic sulfide that we will remove all has hydrophobic property, and molecular size is moderate, so they can be used as the suitable object of cyclodextrin by cyclodextrin cavity institute inclusion, thereby reaches the purpose of organic sulfide removal.
Summary of the invention
The objective of the invention is: in order to simplify the natural gas fine purification sulfur removal technology, improve organic sulfur removal efficient, reduce the refining desulfurization cost, the spy provides a kind of preparation method of natural gas fine purification desulphurizing agent.
In order to achieve the above object, the method that the present invention adopts is: utilize cyclodextrin to prepare natural gas fine purification desulphurizing agent, cyclodextrin molecular in the prepared sweetening agent can be discerned the organosulfur molecules in the Sweet natural gas efficiently, with its inclusion in cyclodextrin cavity, thereby reach the purpose of refining desulfurization.
Technical scheme of the present invention is: a kind of preparation method of natural gas fine purification desulphurizing agent is characterized in that: earlier with AlCl
3With sodium hydroxide be that 1: 3 ratio is dissolved in a certain amount of water in molar ratio, its water is 40～60 with the ratio of solute molar weight, makes Al (OH)
3Colloidal sol; Then to Al (OH)
3Add silicon sol and cyclodextrin in the colloidal sol, its consumption is Al (OH)
3: SiO
2: the mol ratio of cyclodextrin is 0.1: 1: 0.1-1, at room temperature stir and make colloidal sol, churning time 2-6h, mixing speed 1000r/min; Temperature is risen to 60-80 ℃ then, continue stirring reaction 6-20h; Reaction is warming up to 90-130 ℃ of crystallization after finishing, washing at last, dry, compression moulding.Cyclodextrin used in the present invention is a kind of of alpha-cylodextrin, beta-cyclodextrin, γ-Huan Hujing.Present method is with Al (OH)
3, SiO
2, cyclodextrin is 0.1: 1 in molar ratio: the mixed of 0.1-1, and at room temperature stir and make colloidal sol, three's mol ratio is preferably 0.1: 1: 0.4-0.5, churning time is preferably 4-6h, rotating speed 1000r/min; Heat up then and continue reaction, temperature is preferably 65-75 ℃, and the time is preferably 9-16h; Crystallization, washing, drying, compression moulding then, crystallization temperature are preferably 100-110 ℃.
A kind of natural gas fine purification desulphurizing agent sweetening power laboratory evaluation: use by the sweetening agent of above method preparation being 22mg/m through sulphur content after the purifying treatment of natural gas companies
3The organosulfur Sweet natural gas that contains carry out refining desulfurization, the laboratory records with its sulphur content after the sweetening agent desulfurization of beta-cyclodextrin preparation can reach 1.5mg/m
3Below.
The present invention compared with prior art its beneficial effect is: traditional natural gas desulfur method is mostly at removing H
2S carries out, and the technology of organic sulfide removal is less relatively, and removal effect is not good, and what want to reach refining desulfurization requires required desulphurization cost then quite high.The natural gas fine purification desulphurizing agent that the present invention is prepared utilizes the recognition reaction of cyclodextrin hydrophobic cavity to organosulfur molecules, with the organosulfur molecules inclusion in cyclodextrin cavity, thereby reach the purpose of efficient organic sulfide removal; The preparation method of this sweetening agent is simple, and raw material is cheap and easy to get, and can simplify the natural gas fine purification sulfur removal technology, and can effectively reduce the refining desulfurization cost, has a good application prospect.
Embodiment
The present invention is further described below by embodiment.
Embodiment 1
With 0.1molAlCl
3Be dissolved in the 300mL water with 0.3mol sodium hydroxide, make Al (OH)
3Colloidal sol adds then and contains 1molSiO
2Silicon sol and 0.1mol alpha-cylodextrin, at room temperature stir and make colloidal sol, churning time 2h, mixing speed 1000r/min; Temperature is risen to 60 ℃ then, continue stirring reaction 10h; Reaction is warming up to 100 ℃ of crystallization after finishing, washing then, dry, compression moulding.
With by the sweetening agent of above method preparation to being 22mg/m through sulphur content after the purifying treatment of natural gas companies
3The organosulfur Sweet natural gas that contains carry out refining desulfurization, its sulphur content was about 10mg/m after the laboratory recorded desulfurization
3
Embodiment 2
With 0.1molAlCl
3Be dissolved in the 300mL water with 0.3mol sodium hydroxide, make Al (OH)
3Colloidal sol adds then and contains 1molSiO
2Silicon sol and 0.1mol beta-cyclodextrin, at room temperature stir and make colloidal sol, churning time 2h, mixing speed 1000r/min; Temperature is risen to 60 ℃ then, continue stirring reaction 10h; Reaction is warming up to 100 ℃ of crystallization after finishing, washing then, dry, compression moulding.
With by the sweetening agent of above method preparation to being 22mg/m through sulphur content after the purifying treatment of natural gas companies
3The organosulfur Sweet natural gas that contains carry out refining desulfurization, its sulphur content was about 1.5mg/m after the laboratory recorded desulfurization
3
Embodiment 3
With 0.1molAlCl
3Be dissolved in the 300mL water with 0.3mol sodium hydroxide, make Al (OH)
3Colloidal sol adds then and contains 1molSiO
2Silicon sol and 0.1mol γ-Huan Hujing, at room temperature stir and make colloidal sol, churning time 2h, mixing speed 1000r/min; Temperature is risen to 60 ℃ then, continue stirring reaction 10h; Reaction is warming up to 100 ℃ of crystallization after finishing, washing then, dry, compression moulding.
With by the sweetening agent of above method preparation to being 22mg/m through sulphur content after the purifying treatment of natural gas companies
3The organosulfur Sweet natural gas that contains carry out refining desulfurization, its sulphur content was about 6mg/m after the laboratory recorded desulfurization
3
Embodiment 4
With 0.1molAlCl
3Be dissolved in the 350mL water with 0.3mol sodium hydroxide, make Al (OH)
3Colloidal sol adds then and contains 1molSiO
2Silicon sol and 0.2mol beta-cyclodextrin, at room temperature stir and make colloidal sol, churning time 2h, mixing speed 1000r/min; Temperature is risen to 60 ℃ then, continue stirring reaction 10h; Reaction is warming up to 100 ℃ of crystallization after finishing, washing then, dry, compression moulding.
With by the sweetening agent of above method preparation to being 22mg/m through sulphur content after the purifying treatment of natural gas companies
3The organosulfur Sweet natural gas that contains carry out refining desulfurization, its sulphur content was about 1.1mg/m after the laboratory recorded desulfurization
3
Embodiment 5
With 0.1molAlCl
3Be dissolved in the 400mL water with 0.3mol sodium hydroxide, make Al (OH)
3Colloidal sol adds then and contains 1molSiO
2Silicon sol and 0.4mol beta-cyclodextrin, at room temperature stir and make colloidal sol, churning time 2h, mixing speed 1000r/min; Temperature is risen to 60 ℃ then, continue stirring reaction 10h; Reaction is warming up to 100 ℃ of crystallization after finishing, washing then, dry, compression moulding.
With by the sweetening agent of above method preparation to being 22mg/m through sulphur content after the purifying treatment of natural gas companies
3The organosulfur Sweet natural gas that contains carry out refining desulfurization, its sulphur content was about 1.0mg/m after the laboratory recorded desulfurization
3
Embodiment 6
With 0.1molAlCl
3Be dissolved in the 400mL water with 0.3mol sodium hydroxide, make Al (OH)
3Colloidal sol adds then and contains lmolSiO
2Silicon sol and 0.4mol beta-cyclodextrin, at room temperature stir and make colloidal sol, churning time 4h, mixing speed 1000r/min; Temperature is risen to 70 ℃ then, continue stirring reaction 10h; Reaction is warming up to 100 ℃ of crystallization after finishing, washing then, dry, compression moulding.
With by the sweetening agent of above method preparation to being 22mg/m through sulphur content after the purifying treatment of natural gas companies
3The organosulfur Sweet natural gas that contains carry out refining desulfurization, its sulphur content was about 0.95mg/m after the laboratory recorded desulfurization
3
Embodiment 7
With 0.1molAlCl
3Be dissolved in the 400mL water with 0.3mol sodium hydroxide, make Al (OH)
3Colloidal sol adds then and contains 1molSiO
2Silicon sol and 0.4mol beta-cyclodextrin, at room temperature stir and make colloidal sol, churning time 4h, mixing speed 1000r/min; Temperature is risen to 70 ℃ then, continue stirring reaction 10h; Reaction is warming up to 110 ℃ of crystallization after finishing, washing then, dry, compression moulding.
With by the sweetening agent of above method preparation to being 22mg/m through sulphur content after the purifying treatment of natural gas companies
3The organosulfur Sweet natural gas that contains carry out refining desulfurization, its sulphur content was about 0.9mg/m after the laboratory recorded desulfurization
3
Embodiment 8
With 0.1molAlCl
3Be dissolved in the 400mL water with 0.3mol sodium hydroxide, make Al (OH)
3Colloidal sol adds then and contains 1molSiO
2Silicon sol and 0.4mol beta-cyclodextrin, at room temperature stir and make colloidal sol, churning time 4h, mixing speed 1000r/min; Temperature is risen to 80 ℃ then, continue stirring reaction 10h; Reaction is warming up to 110 ℃ of crystallization after finishing, washing then, dry, compression moulding.
With by the sweetening agent of above method preparation to being 22mg/m through sulphur content after the purifying treatment of natural gas companies
3The organosulfur Sweet natural gas that contains carry out refining desulfurization, its sulphur content was about 1.1mg/m after the laboratory recorded desulfurization
3
Claims (3)
1. the preparation method of a natural gas fine purification desulphurizing agent is characterized in that: earlier with AlCl
3With sodium hydroxide be that 1: 3 ratio is dissolved in a certain amount of water in molar ratio, its water is 40～60 with the ratio of solute molar weight, makes Al (OH)
3Colloidal sol; Then to Al (OH)
3Add silicon sol and cyclodextrin in the colloidal sol, its consumption is Al (OH)
3: SiO
2: the mol ratio of cyclodextrin is 0.1: 1: 0.1-1, at room temperature stir and make colloidal sol, churning time 2-6h, mixing speed 1000r/min; Temperature is risen to 60-80 ℃ then, continue stirring reaction 6-20h; Reaction is warming up to 90-130 ℃ of crystallization after finishing, washing at last, dry, compression moulding.
2. the preparation method of natural gas fine purification desulphurizing agent according to claim 1 is characterized in that: employed cyclodextrin is a kind of of alpha-cylodextrin, beta-cyclodextrin, γ-Huan Hujing.
3. the preparation method of natural gas fine purification desulphurizing agent according to claim 1 is characterized in that: with Al (OH)
3Colloidal sol, silicon sol and cyclodextrin mix and make colloidal sol, wherein Al (OH)
3: SiO
2: cyclodextrin three mol ratio is preferably 0.1: 1: 0.4-0.5, and churning time is preferably 4-6h, rotating speed 1000r/min; Heat up then and continue reaction, temperature is preferably 65-75 ℃, and the time is preferably 9-16h; Last crystallization, washing, drying, compression moulding, crystallization temperature is preferably 100-110 ℃.
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| CN101804329A (en) * | 2010-04-22 | 2010-08-18 | 南京工业大学 | Adsorbent for gasoline desulfurization, preparation method thereof and method for gasoline desulfurization by using adsorbent |
| CN102000544A (en) * | 2010-11-30 | 2011-04-06 | 南京工业大学 | Adsorbent for gasoline desulfurization, preparation method thereof and application thereof in gasoline desulfurization |
| CN104667872A (en) * | 2015-02-12 | 2015-06-03 | 江苏竹海活性炭有限公司 | High-efficiency deep desulfurization active carbon and preparation method thereof |
| CN104870617A (en) * | 2012-12-27 | 2015-08-26 | 国际壳牌研究有限公司 | Compositions |
| CN105126768A (en) * | 2015-09-11 | 2015-12-09 | 中国石油大学(华东) | Light-weight oil desulfurizing agent based on supra-molecular inclusion effect and application method thereof |
| CN111763503A (en) * | 2020-07-10 | 2020-10-13 | 西南石油大学 | Hydrogen sulfide inhibitor for drilling fluid and preparation method thereof |
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| CN1133731C (en) * | 2001-03-24 | 2004-01-07 | 太原理工大学 | Coarse iron oxide desulfurizer for high temperature gas and its prepn |
| CN1172850C (en) * | 2001-07-06 | 2004-10-27 | 青岛海洋化工集团公司 | Method for producing silico-aluminium gelatinized granule product |
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| CN101804329A (en) * | 2010-04-22 | 2010-08-18 | 南京工业大学 | Adsorbent for gasoline desulfurization, preparation method thereof and method for gasoline desulfurization by using adsorbent |
| CN102000544A (en) * | 2010-11-30 | 2011-04-06 | 南京工业大学 | Adsorbent for gasoline desulfurization, preparation method thereof and application thereof in gasoline desulfurization |
| CN102000544B (en) * | 2010-11-30 | 2012-11-21 | 南京工业大学 | Adsorbent for gasoline desulfurization, preparation method thereof and application thereof in gasoline desulfurization |
| CN104870617A (en) * | 2012-12-27 | 2015-08-26 | 国际壳牌研究有限公司 | Compositions |
| CN104667872A (en) * | 2015-02-12 | 2015-06-03 | 江苏竹海活性炭有限公司 | High-efficiency deep desulfurization active carbon and preparation method thereof |
| CN104667872B (en) * | 2015-02-12 | 2017-03-08 | 江苏竹海活性炭有限公司 | A kind of efficient deep desulfuration activated carbon and preparation method thereof |
| CN105126768A (en) * | 2015-09-11 | 2015-12-09 | 中国石油大学(华东) | Light-weight oil desulfurizing agent based on supra-molecular inclusion effect and application method thereof |
| CN105126768B (en) * | 2015-09-11 | 2018-08-21 | 中国石油大学(华东) | A kind of Light Oil Desulfurization agent and its application method based on supermolecule clathration |
| CN111763503A (en) * | 2020-07-10 | 2020-10-13 | 西南石油大学 | Hydrogen sulfide inhibitor for drilling fluid and preparation method thereof |
| CN112080222A (en) * | 2020-09-25 | 2020-12-15 | 陈宁 | Environment-friendly multifunctional stabilizer and preparation method thereof |
| CN112080222B (en) * | 2020-09-25 | 2022-06-10 | 陈宁 | Environment-friendly multifunctional stabilizer and preparation method thereof |
| CN114471528A (en) * | 2022-03-21 | 2022-05-13 | 西南石油大学 | High-sulfur natural gas direct conversion material and large-scale preparation method and application thereof |
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Application publication date: 20080611 Assignee: QINGDAO XINAO XINCHENG GAS CO., LTD. Assignor: Southwest Petroleum University Contract record no.: 2012370000183 Denomination of invention: Production method of natural gas fine purification desulphurizing agent Granted publication date: 20100602 License type: Exclusive License Record date: 20120726 |
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