CN100415345C - Preparation of composite acid gas absorbent - Google Patents
Preparation of composite acid gas absorbent Download PDFInfo
- Publication number
- CN100415345C CN100415345C CNB2005100409955A CN200510040995A CN100415345C CN 100415345 C CN100415345 C CN 100415345C CN B2005100409955 A CNB2005100409955 A CN B2005100409955A CN 200510040995 A CN200510040995 A CN 200510040995A CN 100415345 C CN100415345 C CN 100415345C
- Authority
- CN
- China
- Prior art keywords
- preparation
- cooled
- calcination
- acid gas
- temperature
- 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
Links
Images
Landscapes
- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
A processs for preparing the composite acidic gas absorbent used to prepare catalyst includes such steps as pulverizing porous silicon gel, sieving, drying, calcining, cooling, sequentially immersing in the aqueous solution of nickel nitrate and copper nitrate, and the aqueous solution of phospho-tungstic acid, laying aside, drying, slow calcining, coaling, heating the refractory inertial material to a certain temp, using N2 to displace the air in system, adding H2 and ethanolamine to evaporator of material, evaporating, catalytic reaction on gas-phase flowing material to obtain resultant, condensing to obtain liquid phase and separating H2.
Description
One, technical field
The invention belongs to the preparation method of catalysis synthetic and separation field, particularly a kind of composite acid gas absorbent.
Two, background technology
The composite acid gas absorbent compatibility premium properties of single solution, higher mass transfer force, higher absorptive capacity, higher absorption rate and regeneration rate can be provided in separation process.At present as absorb the various composite solutions of sour gas industrial obtained extensive use (Chemical Engineering Science, 2001,56:6217-6224).Patent US 4,397,660, DE3, propositions such as 411,532 be double solvents.US4,892,674 propose to add steric hindrance amine salt or steric hindrance amino acid formation double solvents in pure amine solvent; US4,895,670 propose at sterically hindered amines and the amino acids formed double solvents of steric hindrance.CN1356157A proposes a kind of mixed solvent and is made up of MDEA (N methyldiethanol amine) and a kind of sterically hindered amines.CN1354036A proposes a kind of compound amine solvent and is made up of MEA (monoethanolamine) and a kind of reactive amines.The forming process of these composite solutions is physical mixing processes, be about to (prescription) mixing according to a certain percentage of two or three solvent and form mixed solution, and one or both solvent markets in the composite solution is difficult for buying usually, synthetic cost height.
Three, summary of the invention
The object of the present invention is to provide a kind of method for preparing composite acid gas absorbent by chemical synthesis.
The technical scheme that realizes the object of the invention is: a kind of preparation method of composite acid gas absorbent is characterized in that may further comprise the steps:
1.1 Preparation of Catalyst: at first Bio-sil is pulverized sub-sieve, get 10～50 order particles, dry back calcination 4～6h in 400～700 ℃ Muffle furnace takes out and is cooled to room temperature; Bio-sil after the calcination is immersed in the solution of nickel nitrate, copper nitrate, secondary deionized water, leaves standstill the back drying, and cooling is cooled to room temperature gradually after Muffle furnace slowly heats up calcination; And then be immersed in the solution of phosphotungstic acid, secondary deionized water, leaving standstill the back drying, natural rate of temperature fall is cooled to room temperature after Muffle furnace slowly heats up calcination; Put into the catalytic synthesis device at last, the H under 150～250 ℃
2Reduce in the stream; In the catalyst for preparing, the mass percent of Ni, Cu and phosphotungstic acid is 25～65: 5～25: 0.1～1.0;
1.2 absorbent is synthetic: be warmed up to target temperature constant temperature after the heatproof inert material is put into the material vaporizer, behind the air in the complete exchange system of nitrogen, add hydrogen and feed ethanol amine to the material vaporizer, the vaporization back enters in the catalytic synthesis device with gaseous stream, carry out the catalytic reaction synthetic product, this product is a liquid phase material through condenser condenses, after the collection hydrogen is separated with product, hydrogen reclaims, and liquid phase material is compound absorbent; The H that the material vaporizer adds
2With feed ethanol amine mol ratio be 0.1～1.8, the total flow 10～30L/h of gas phase mixture.
The preparation method of composite acid gas absorbent of the present invention, leave standstill behind 20～50h dryly, after Muffle furnace slowly is warming up to 500～600 ℃ of calcination 4～6h, be cooled to 200 ℃ with the rate of temperature fall of 0.5～2 ℃/min, keep 2h at 200 ℃, be cooled to room temperature with 0.5～1 ℃/min again.
The preparation method of composite acid gas absorbent of the present invention, the reaction temperature of catalytic synthesis device are 150～320 ℃, and pressure is 0.4～0.8MPa.
Compared with prior art, remarkable advantage of the present invention is: the catalyst n iCu/SiO that a kind of gas phase catalysis that the present invention proposes is synthetic
2+ trace amounts of phosphorus wolframic acid not only has good catalytic performance, and the abundant raw material of preparation catalyst, and cheap, the preparation method is simple, and synthesis technique realizes that easily product cost is lower; The product composite acid gas absorbent of preparation can also can be used as the additive of other absorbent directly as acid gas absorbent; Can be applied to the directly reactor of contact of gas-liquid,, also can be applied in the film absorption technique (being membrane contactor) as packed tower and plate column etc.
Four, description of drawings
Fig. 1 is the preparation method's of a composite acid gas absorbent of the present invention Preparation of Catalyst flow chart.
Fig. 2 is the preparation method's of a composite acid gas absorbent of the present invention technology synthetic schemes.
Five, the specific embodiment
Below in conjunction with accompanying drawing the present invention is described in further detail.
In conjunction with Fig. 1, Fig. 2, the preparation method of composite acid gas absorbent of the present invention may further comprise the steps:
(1) at first Bio-sil is pulverized, sub-sieve is got 10～50 order particles, 20～30 order particles preferably, and dry 3h under 120 ℃ of temperature, 650 ℃ temperature lower calcination 4h in Muffle furnace takes out, and is cooled to room temperature in drier.
(2) get nickel nitrate (Ni (NO
3)
26H
2O) 446g and copper nitrate (Cu (NO
3)
23H
2O) 112g is water-soluble, and finished product 200g in (1) be impregnated in the solution of being prepared, and leaves standstill 24h after fully mixing.Place 60～70 ℃ of water-baths then, stir evaporation drying down, evaporate fully until moisture, dry 4h under 120 ℃ slowly is warming up to 500 ℃ at Muffle furnace, and calcination 4h.Rate of temperature fall with 2 ℃/min is cooled to 200 ℃, keeps 2h at 200 ℃, is cooled to room temperature with 1 ℃/min again.
(3) get phosphotungstic acid (2H
3PO
424WO
348H
2O) 2.5g is water-soluble, and the finished product in (2) be impregnated in the solution of being prepared, and leaves standstill 20h.Place 60～70 ℃ of water-baths then, stir evaporation drying down, evaporate fully until moisture, dry 4h under 120 ℃ slowly is warming up to 500 ℃ at Muffle furnace, and calcination 4h.Be cooled to room temperature with natural rate of temperature fall, the catalyst quality ratio of preparation is: Ni 30%, and Cu 10%, phosphotungstic acid 0.5%.
(4) get (3) finished product catalytic synthesis device of packing into, under 200 ℃, 15L/h H
2Reduce 1～2h in the stream.
(5) with the heatproof inert material, be warmed up to target temperature constant temperature after putting into the material vaporizer as quartz sand, this target temperature is 200～300 ℃, uses N
2The about 3～5min of air in the gas displacement synthesis system.Feed hydrogen and feed ethanol amine (MEA), H to the material vaporizer
2With the mol ratio of monoethanolamine 0.55, flow 20L/h, catalytic synthesis device reaction temperature is 200 ℃, pressure is 0.5MPa, the product logistics is condensed into liquid phase material through air cooler, after the collection hydrogen is separated with product, and hydrogen reclaims, liquid phase material is compound absorbent, and the synthetic compound absorbent component that obtains is: piperazine (C
4H
8(NH)
2), monoethanolamine (NH
2C
2H
4OH), beta-hydroxyethyl monoethanolamine (NH
2C
2H
4NHC
2H
4OH).
Claims (3)
1. the preparation method of a composite acid gas absorbent is characterized in that may further comprise the steps:
1.1 Preparation of Catalyst: at first Bio-sil is pulverized sub-sieve, get 10～50 order particles, dry back calcination 4～6h in 400～700 ℃ Muffle furnace takes out and is cooled to room temperature; Bio-sil after the calcination is immersed in the solution of nickel nitrate, copper nitrate, secondary deionized water, leaves standstill the back drying, and cooling is cooled to room temperature gradually after Muffle furnace slowly heats up calcination; And then be immersed in the solution of phosphotungstic acid, secondary deionized water, leaving standstill the back drying, natural rate of temperature fall is cooled to room temperature after Muffle furnace slowly heats up calcination; Put into the catalytic synthesis device at last, the H under 150～250 ℃
2Reduce in the stream; In the catalyst for preparing, the mass ratio of Ni, Cu and phosphotungstic acid is: 25%～65%: 5%～25%: 0.1%～1.0%;
1.2 absorbent is synthetic: be warmed up to target temperature constant temperature after the heatproof inert material is put into the material vaporizer, behind the air in the complete exchange system of nitrogen, add hydrogen and feed ethanol amine to the material vaporizer, the vaporization back enters in the catalytic synthesis device with gaseous stream, carry out the catalytic reaction synthetic product, this product is a liquid phase material through condenser condenses, after the collection hydrogen is separated with product, hydrogen reclaims, and liquid phase material is compound absorbent; The H that the material vaporizer adds
2With feed ethanol amine mole be than 0.1～1.8, the total flow 10～30L/h of gas phase mixture.
2. the preparation method of composite acid gas absorbent according to claim 1, it is characterized in that leaving standstill behind 20～50h dry, after Muffle furnace slowly is warming up to 500～600 ℃ of calcination 4～6h, rate of temperature fall with 0.5～2 ℃/min is cooled to 200 ℃, keep 2h at 200 ℃, be cooled to room temperature with 0.5～1 ℃/min again.
3. the preparation method of composite acid gas absorbent according to claim 1, the reaction temperature that it is characterized in that the catalytic synthesis device is 150～320 ℃, pressure is 0.4～0.8MPa.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100409955A CN100415345C (en) | 2005-07-12 | 2005-07-12 | Preparation of composite acid gas absorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100409955A CN100415345C (en) | 2005-07-12 | 2005-07-12 | Preparation of composite acid gas absorbent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1895739A CN1895739A (en) | 2007-01-17 |
| CN100415345C true CN100415345C (en) | 2008-09-03 |
Family
ID=37608470
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100409955A Expired - Fee Related CN100415345C (en) | 2005-07-12 | 2005-07-12 | Preparation of composite acid gas absorbent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100415345C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102895985B (en) * | 2012-10-10 | 2015-04-01 | 南京信息工程大学 | Catalyst for synthesizing acidic gas absorbent and preparation method for catalyst |
| CN102895978B (en) * | 2012-10-19 | 2014-11-12 | 南京信息工程大学 | Catalyst used for synthetizing polyamino compound and preparation method for catalyst and application of catalyst |
| CN109852974B (en) * | 2019-04-08 | 2020-11-03 | 上海金兆节能科技有限公司 | Antirust cleaning agent composition and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85103855A (en) * | 1985-05-08 | 1986-11-05 | 南京化学工业公司研究院 | Removing of CO 2 by potassium carbonate solution with complex catalysts |
| CN1034198A (en) * | 1987-11-06 | 1989-07-26 | 日本触媒化学工业株式会社 | Acid gas absorbent composition |
| US4892674A (en) * | 1987-10-13 | 1990-01-09 | Exxon Research And Engineering Company | Addition of severely-hindered amine salts and/or aminoacids to non-hindered amine solutions for the absorption of H2 S |
| US4895670A (en) * | 1987-10-13 | 1990-01-23 | Exxon Research And Engineering Company | Addition of severely-hindered aminoacids to severely-hindered amines for the absorption of H2 S |
| CN1056259A (en) * | 1990-04-28 | 1991-11-20 | 南京化学工业公司研究院 | The method of purification of acidic gas |
| CN1349427A (en) * | 1999-05-03 | 2002-05-15 | 联合碳化物化学和塑料技术公司 | Absorbent compositions for the removal of acid gases from the gas streams |
| CN1356158A (en) * | 2001-09-26 | 2002-07-03 | 南化集团研究院 | Physical process for removing sulfur and carbon by solvent |
-
2005
- 2005-07-12 CN CNB2005100409955A patent/CN100415345C/en not_active Expired - Fee Related
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN85103855A (en) * | 1985-05-08 | 1986-11-05 | 南京化学工业公司研究院 | Removing of CO 2 by potassium carbonate solution with complex catalysts |
| US4892674A (en) * | 1987-10-13 | 1990-01-09 | Exxon Research And Engineering Company | Addition of severely-hindered amine salts and/or aminoacids to non-hindered amine solutions for the absorption of H2 S |
| US4895670A (en) * | 1987-10-13 | 1990-01-23 | Exxon Research And Engineering Company | Addition of severely-hindered aminoacids to severely-hindered amines for the absorption of H2 S |
| CN1034198A (en) * | 1987-11-06 | 1989-07-26 | 日本触媒化学工业株式会社 | Acid gas absorbent composition |
| CN1056259A (en) * | 1990-04-28 | 1991-11-20 | 南京化学工业公司研究院 | The method of purification of acidic gas |
| CN1349427A (en) * | 1999-05-03 | 2002-05-15 | 联合碳化物化学和塑料技术公司 | Absorbent compositions for the removal of acid gases from the gas streams |
| CN1356158A (en) * | 2001-09-26 | 2002-07-03 | 南化集团研究院 | Physical process for removing sulfur and carbon by solvent |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1895739A (en) | 2007-01-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Progress and current challenges for CO2 capture materials from ambient air | |
| KR101253985B1 (en) | Porous organic-inorganic hybrid materials, method for preparing thereof, adsorbant comprising them and application thereof | |
| US20170158837A1 (en) | Porous polymer material | |
| Li et al. | Energy efficient catalytic CO2 desorption: mechanism, technological progress and perspective | |
| US20110311429A1 (en) | Method for Removing CO2 from Coal-Fired Power Plant Flue Gas Using Ammonia as the Scrubbing Solution, with a Chemical Additive for Reducing NH3 Losses, Coupled with a Membrane for Concentrating the CO2 Stream to the Gas Stripper | |
| CN113210021B (en) | Transition metal-based composite catalyst for promoting desorption of carbon dioxide rich solution, and preparation method and application thereof | |
| Lan et al. | Highly efficient, selective and reversible capture of sulfur dioxide by methylated-polyethylenimine supported on graphitic carbon nitride | |
| KR20120021899A (en) | Porous organic-inorganic hybrid materials, method for preparing thereof, adsorbant comprising them and application thereof | |
| CN100415345C (en) | Preparation of composite acid gas absorbent | |
| JP2006036950A (en) | Gas purification process and absorbent solution used in the same | |
| Huang et al. | Study on the efficiency of multiple amino groups in ionic liquids on their sorbents performance for low-temperature CO2 capture | |
| CN110339672B (en) | Functionalized ionic liquid/organic solvent composite system and preparation method and application thereof | |
| CN110681410B (en) | For enriching CO 2 Preparation method of SBA-15 molecular sieve based supported catalyst for desorbing amine solution | |
| CN116585868A (en) | Integrated process for capturing carbon dioxide and preparing urea | |
| CN113277520B (en) | Silicon dioxide mesoporous material and preparation method and application thereof | |
| CN106984137A (en) | A kind of absorption CO of phase separation2Polyaminoacid ionic liquid preparation and its application method | |
| Fu et al. | Dispersing LiCl in zwitterionic COF for highly efficient ammonia storage and separation | |
| CN111871152B (en) | Functionalized ionic liquid and preparation method and application thereof | |
| CN113244881A (en) | Method for preparing lithium orthosilicate material by taking KIT-6 as silicon source, modification and application thereof | |
| US11548789B2 (en) | Stable ammonia absorbents | |
| CN115945033A (en) | Absorb CO 2 Low mucus-solid phase transition function ionic solvent of | |
| Hao et al. | Selective adsorption of CO 2 on amino-functionalized silica spheres with centrosymmetric radial mesopores and high amino loading | |
| CN102895985B (en) | Catalyst for synthesizing acidic gas absorbent and preparation method for catalyst | |
| CN101254453A (en) | Preparation of high-temperature adsorbing agent for simultaneously removing portion gas in stack gas | |
| KR101935483B1 (en) | Method for Manufacturing Magnesium Oxide Adsorbent for Capturing Carbon Dioxide by Combustion of Fuel |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20080903 Termination date: 20110712 |