CN1113828A - high efficiency carbon monoxide adsorbent - Google Patents
high efficiency carbon monoxide adsorbent Download PDFInfo
- Publication number
- CN1113828A CN1113828A CN 94110288 CN94110288A CN1113828A CN 1113828 A CN1113828 A CN 1113828A CN 94110288 CN94110288 CN 94110288 CN 94110288 A CN94110288 A CN 94110288A CN 1113828 A CN1113828 A CN 1113828A
- Authority
- CN
- China
- Prior art keywords
- adsorbent
- ion
- under
- exchange
- hour
- 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.)
- Pending
Links
Images
Landscapes
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The present invention relates to a high-effective CO a dsorbent applied to recover high-purity CO from industrial waste gas. It is characterized by that it uses industrial water glass, aluminium hydroxide or aluminium sulfate, alkali and a certain quantity of Ca(++) and Mg(++) as raw materials, and uses a crystallization orienting agent technique, and uses the high-silicon octahedral zeolite which is hydro-thermally-synthesized by using ingredient gel prepared according to its ingredient gram molecular ratio of (3.0-8.0) N2O:Al2O3:(7.0-18) SiO2:(170-359)H2O as the crrier, and makes the above-mentioned materials and copper nitrate solution or cupric chloride solution pass through the processes of ion-exchange treatment and impregnation treatment so as to obtain the invented product. Its CO adsorption capacity is high, and CO2 adsorption capacity is low.
Description
Along with C
1Developing rapidly of chemistry, the development of CO is increasingly extensive.CO the more important thing is also to can be used to synthesize basic organic chemical industry's product of being badly in need of on the various markets except that as fuel and the metallic reducing gas, as methyl alcohol, alkene and phosgene etc., is organic chemical industry's developing direction.The whole world contains industrial waste gas a lot of blast furnace gas, converter gas and the oven gas as steel mill of CO at present, and it is mainly composed as follows: H
252%; CH
424%; CO 104%; N
2+ O
27%; CO
23%C
2H
42.3%; H
2S69mg/M
3NO 0.5～0.8ppm.Form in view of the above, we have done following measuring and calculating, and promptly a synthesis ammonia plant is if consume oven gas 100 myriametres, H wherein every day
2Gas can be produced No. 263, synthetic ammonia (theoretical value), also has 10.4 myriametres
3CO if recycled, making it turns waste into wealth, and can produce 154.5 tons of synthesizing methanols again, its economic benefit is appreciable.On the technology that reclaims CO, traditional separation by deep refrigeration reclaims separation because apparatus expensive can not satisfy the CO of middle and small scale.If using efficiently, the CO of the pressure swing adsorption method recovery separating high-purity of zeolite adsorbents has the unrivaled superiority of traditional handicraft.But the key that realizes this technology is to develop novel efficient CO adsorbent.In recent years, NKK (NKK) is a raw material with NaY stone, and the method for modifying that adopts ion-exchange and dipping to combine has been developed a kind of CuCl
2The CU(I) the y-type zeolite adsorbent, the adsorbance to CO is 45(ml/g at normal temperatures and pressures).
The object of the present invention is to provide a kind of efficient CO adsorbent, it can reclaim highly purified CO from industrial waste gas, and adsorbance is big, the efficient height.
The invention provides a kind of efficient CO adsorbent, be applicable to and reclaim highly purified CO from industrial waste gas, is by containing Ca
2+, Mg
2+The faujasite of ion is through Cu
2Salting liquid carries out ion-exchanged and obtains, and it consists of (weight, below all with) Cao content (12～14) %, SiO
2/ Al
2O
3Be 4.0～5.0, Na
2O content＜1.0%; CaO content 0.1～1.0, MgO content 0.1～1.2% is characterized in that this adsorbent is prepared by following method: the preparation of (1) carrier:
With industry water glass, aluminium hydroxide or aluminum sulfate, alkali and a certain amount of Ca
2+And Mg
2Be raw material, adopt the crystallization director technology;
Reactant gel batching mole ratio is (3.0～8.0) Na
2O: Al
2O
3: (7.0～18) SiO
2: (170～350) H
2O
Crystallization director accounts for 2～10% of total amount.
Hydro-thermal synthesizes and contains Ca under 353～393K condition
2+, Mg
2+The high silicon faujasite of ion;
(2) ion-exchanged
High silicon faujasite carrier that is synthesized and copper nitrate solution＜are carried out ion-exchange, the Cu of its exchange liquid at PH in 7.0 the exchanging liquid
2+/ Na
+Between 0.30～1.00, concentration is between 0.1～0.6M, and temperature is between 353～373K; After under washing 323K～423K, oven dry in 1～4 hour, under 553K～843K, roasting in 1～4 hour makes Cu
2+Modification contain Ca
2+, Mg
2+The faujasite of ion;
(3) reduction
H at 0.2～10.0KPa
2Or in the CO atmosphere, between 473～773K, reduced 1～4 hour.
When one-step method prepared efficient CO adsorbent, high silicon faujasite and copper nitrate solution preferably exchanged 2～4 times repeatedly, 1～4 hour swap time, exchange degree〉90%.When adopting two-step method to prepare efficient CO adsorbent, ion-exchange is to its exchange degree〉after 48%, the oven dry roasting is used concentration between the copper chloride solution of 0.1～0.5M clear 0.5～2.0 hour again, evaporate to dryness under 323K～423K again, roasting under 558K～843K.
The present invention also provides a kind of practical in industry CO adsorbent, it is characterized in that, with above-mentioned efficient CO adsorbent and adhesive (SiO
2, Al
2O
3, SiO
2～Al
2O
3Or the sweet soil of sheep) mix with the proportioning of 2%～10% scope, add then less than its total amount 5% expanding agent (four cyanines powder) and an amount of water, even through mechanical mixture, last shaping and drying and roasting make.
Below by the present invention of example enumeration.
Accompanying drawing 2 is under 293K, CO and CO
2Adsorption isotherm on ACM-2-0, ACM-2-2, ACM-2-3 and ACM-2-1 adsorbent;
Accompanying drawing 3 under different temperatures, the adsorption isotherm of CO on the LACM of practical in industry adsorbent;
Accompanying drawing 4 under different pressures, the adsorption isobar of CO on the LACM of practical in industry adsorbent;
Accompanying drawing 5 under different adsorbances, the adsorption isostere of CO on the LACM of practical in industry adsorbent;
Accompanying drawing 6 under different adsorbances, LnP that CO adsorbs on the LACM of practical in industry adsorbent and the relation of 1/T;
Accompanying drawing 7 is under 293K, time relation when the adsorbance of CO on the LACM of practical in industry adsorbent and absorption.
Example 1
With industry water glass, aluminium hydroxide, alkali and adding proper C a
2+, Mg
2+Ion is a raw material, is 6Na by the batching mole ratio of reactant gel
2O: Al
2O
3: 16SiO
2: 320H
2O.The batching mole ratio of crystallization director is 16Na
2O: Al
2O
3: 15SiO
2: 320H
2O.Behind crystallization guiding gel, under room temperature, wore out 5 hours, add in the reactant gel that just has been made into 5% ratio thereupon, stir and be placed in the autoclave, be warmed up to 373K and make its crystallization 24 hours, obtained good, the of uniform size crystal of degree of crystallinity, wash with water to PH be 8～9, after filter doing, successively dry and 2 hours under 383K and 823K respectively, then make a kind of Ca of containing
2+And Mg
2+The high silicon Na type octahedrite crystal of ion.Its SiO
2/ Al
2O
3Greater than 4.4; Phenenyl absorbing amount is greater than 250(mg/g); CaO content is that 0.625(is heavy); MgO content is that 0.34%(is heavy).
Example 2
Take by weighing the product adding 2.18 gram copper nitrate (Cu (NO that 5 gram examples 1 are made
3)
23H
2O) be dissolved in 30 milliliters the solution, ion-exchange is 2 hours between 363K～373K, exchange repeatedly 3 times, with chemical water washing 5～10 times, drying is 2 hours under 393K, after compressing tablet, moulding, pulverizing and sieve, get the roasting 2 hours under 573K of sample particle between 26～40 orders, at last under 623K, reductase 12 hour in the CO of 6.67KPa atmosphere, then the product of efficient CO adsorbent of one-step method preparation, it is heavy wherein to contain CuO 13.01%(), CaO 0.56%(is heavy) and MgO 0.25%(heavy).Its production code member is ACM-2-0.
Example 3
Product 5 grams of one step method for making are added 0.310 gram CuCl
22H
2O
2Be dissolved in the beaker of suitable quantity of water, flood half an hour under the room temperature, then between 353K～373K at leisure evaporation do, at get down from horse not kiln roasting 2 hours of 573K, it is heavy wherein to contain CuO 14.8%(again), CaO 0.53%(is heavy) and MgO 0.22%(heavy).Behind compression molding and crushing screening, get the granular mouth between 26～40 orders, under 623K, reductase 12 hour in the CO of 6.67KPa atmosphere is the efficient CO adsorbent of two-step method preparation, and it numbers adsorbent, and it is numbered ACM-2-2.
Example 4
Take by weighing one-step method by example 2() preparation Cu
2+, Ca
2+And Mg
2+The 5 gram addings of octahedrite adsorbent fill with 0.460 gram CuCl
22H
2O is made in the beaker of debita spissitudo solution, floods half an hour under the room temperature, and then the efficient CO adsorbent made from example 3 identical steps.It is heavy wherein to contain CuO 15.1%(), CaO 0.49%(is heavy) and MgO 0.20%(heavy).Its production code member is ACM-2-3.
Example 5
The same example 4 of method for making just adds CuCl
22H
2O amount be 1/3 of an example 4 only, and the CuO in the product is that 13.9%(is heavy), CaO 0.50%(is heavy) and MgO 0.24%(weight).Its production code member is ACM-2-1.
List in table 1 by example 1 to the four kinds of efficient CO adsorbent of difference CO performances and traditional X, the CO absorption performance of Y zeolite of example 5.
Example 6
80/20 ratio batching with the efficient CO absorption of the method preparation identical and the sweet soil of some mixture sheep in its weight ratio with example 3, it is heavy to add 5%(again) the sesbania powder as expanding agent, through fully mixing, compression molding, roasting and crushing screening then, get particulate samples (its average particulate diameter is 0.0575 centimetre) between 26～40 orders under 623K, reductase 12 hour in the CO of 6.67KPa atmosphere, be practical in industry, contain Cu
2+, Ca
2+And Mg
2+The efficient CO adsorbent of ion, it is heavy wherein to contain CuO 11.8%(), CaO 0.41%(is heavy) and MgO 0.17%(heavy).Production code member is LACM-2-2.
Example 7
The absorption potential mechanics and dynamic (dynamical) parameter evaluation of efficient CO adsorbent: the efficient CO adsorbent of all kinds of above-mentioned preparation has carried out comprehensive research to CO absorption affinity thermodynamics and some basic parameters that adsorb power and each other related thereof on the BET vacuum plant of the CAHN-2000 type vacuum electricity Libra that u.s. export is housed.Its result is shown in its table 1 respectively, and 2,3,4 and 5 and accompanying drawing.
Under table 1 different temperatures, the adsorption isotherm data of prepared CO adsorbent
Under table 2 different temperatures, the LACM adsorbent of practical in industry is to the adsorption isotherm data of CO
Under the different equalizing pressures of table 3, the LACM adsorbent of practical in industry is to the adsorption isobar data of CO
Table 4, under the different adsorbances, the LACM adsorbent of practical in industry is to the adsorption isostere data of CO
Fig. 1,2 show that the prepared several compound efficient CO adsorbent of (1) the present invention has the raising of highly significant than traditional X, Y zeolite to the CO adsorbance, otherwise, to CO
2Adsorbance but obviously reduce.Under at 293K, CO and CO
2Equalizing pressure when being 6.67KPa, the ACM-2-0 adsorbent is 86.7 (ml/g) to the adsorbance of CO, and y-type zeolite has only 7(ml/g), the former has increased by 11.4 times than the latter, with regard to CO
2Absorption, the adsorbance of ACM-2-0 is 26(ml/g), and y-type zeolite is 52(ml/g), the former has reduced half on the contrary than the latter.The efficient CO adsorbent that this phenomenon explanation is synthesized is very beneficial for reclaiming highly purified CO from industrial waste gas.(2) under low CO equalizing pressure, obviously greater than the (see figure 2) of two-step method preparation, this shows that it more helps being used for purifying and contains the gas of trace amounts of CO impurity to the ACM-2-0 adsorbent of one-step method preparation to the adsorbance of CO.
Under given CO adsorbance, InP all becomes good linear relationship with 1/T to Fig. 6 as can be known.Therefore, can utilize the Clapeyron-Clausins equation to measure the isosteric heat of adsorption of CO at this adsorbent surface.
InP=Q
wt/R·1/T+C
The LACM adsorbent that the formula surveyed industry is practical to the adsorbance of CO, fill up rate (θ=a/a
∞) and heat of adsorption between relation list in table 5.
The LACM adsorbent of table 5 practical in industry to the adsorbance of CO, fill up the relation between rate and the heat of adsorption
（θ=a/a
∞a
∞=53.8ml/g）
Fig. 7 as can be known by CO under 293K, its pressure is the dividing potential drop that this pressure of 10.13KPa(is equivalent to CO in the oven gas) time, each the experimental point data on the curve of adsorption kinetics on the LACM of the practical in industry adsorbent are found In (Q
∞-Q
t/ Q
∞-Q
0) with adsorption time t between become good linear In (Q
∞-Q
t/ Q
∞-Q
0)=In (6/ π
2)-(D π
2/ a
2) t
Q in the formula
∞, Q
tWith Q
0Be respectively adsorption time and be the adsorbance of ∞, t and at 0 o'clock; A is the particle diameter (0.0575 centimetre) of adsorbent.According to the slope of this linear relationship, determine the diffusivity (D/a of CO on the LACM of practical in industry adsorbent
2) be 1.93 * 10
-3Second
-1, its diffusion coefficient D is 6.38 * 10
-6(centimetre
2/ second).
Claims (4)
1, a kind of efficient CO adsorbent is applicable to and reclaims highly purified CO from industrial waste gas, is by containing Ca
++, Mg
++The faujasite of ion is through Cu
2+Salting liquid carries out ion-exchanged and obtains, and it consists of (weight) CaO content (12～14) %, SiO
2/ Al
2O
3Be 4.0～5.0, Na
2O content＜1.0%, CaO content 0.1～1.0%, MgO content 0.1～1.2% is characterized in that this adsorbent is prepared by following method:
(1) carrier preparation:
With industry water glass, aluminium hydroxide or aluminum sulfate, alkali and a certain amount of Ca
2+And Mg
2+Be raw material, adopt the crystallization director technology;
Reactant gel batching mole ratio is (3.0～8.0) Na
2O: Al
2O
3: (7.0～18) SiO
2: (170～350) H
2O
Crystallization director batching mole ratio is (5～16) Na
2O: Al
2O
3: (3.5～15) SiO
2: (200～300) H
2O
Hydro-thermal synthesizes and contains Ca under 353～393K condition
2+, Mg
2+The high silicon faujasite of ion;
(2) ion-exchanged
High silicon faujasite carrier that is synthesized and copper nitrate solution are carried out ion-exchange in the exchanging liquid of PH＜7.0, the Cu of its exchange liquid
2+/ Na
+Between 0.30～1.00, concentration is between 0.1～0.6M, and temperature is between 353～373K; After washing, under 323K～423K, oven dry in 1～4 hour, under 553K～843K, roasting in 1～4 hour makes Cu
2+Modification contain Ca
2+, Mg
2+The composite efficient adsorbent of ion;
(3) reduction
H at 0.2～10.0KPa
2Or in the CO atmosphere, between 473～773K, reduced 1～4 hour.
2, by the described efficient CO adsorbent of claim 1, it is characterized in that: high silicon faujasite and copper nitrate solution preferably exchange 2～4 times repeatedly, 1～4 hour swap time, exchange degree〉90%.
3, by the described efficient CO adsorbent of claim 1, it is characterized in that ion-exchange arrives its exchange degree〉after 48%, the oven dry roasting is used concentration between the copper chloride solution of 0.1～0.5M clear 0.5～2.0 hour again, evaporate to dryness under 323K～423K again, roasting under 558K～843K.
4, a kind of practical in industry adsorbent is characterized in that, with described efficient CO adsorbent of claim 1～3 and adhesive (SiO
2, Al
2O
3, SiO
2～Al
2O
3Or the sweet soil of sheep) mix with the proportioning of 2%～10% scope, add then less than its total amount 5% expanding agent (four cyanines powder) and an amount of water, even through mechanical mixture, last shaping and drying and roasting make.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94110288 CN1113828A (en) | 1994-05-31 | 1994-05-31 | high efficiency carbon monoxide adsorbent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 94110288 CN1113828A (en) | 1994-05-31 | 1994-05-31 | high efficiency carbon monoxide adsorbent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1113828A true CN1113828A (en) | 1995-12-27 |
Family
ID=5034268
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 94110288 Pending CN1113828A (en) | 1994-05-31 | 1994-05-31 | high efficiency carbon monoxide adsorbent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1113828A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100471555C (en) * | 2005-05-25 | 2009-03-25 | 太原理工大学 | Process for preparing adsorbent of molecular sieve with high adsorption value fluorite |
-
1994
- 1994-05-31 CN CN 94110288 patent/CN1113828A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100471555C (en) * | 2005-05-25 | 2009-03-25 | 太原理工大学 | Process for preparing adsorbent of molecular sieve with high adsorption value fluorite |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1148025B1 (en) | Method for purifying hydrogen-based gas mixture | |
| Kunecki et al. | Synthesis of faujasite (FAU) and tschernichite (LTA) type zeolites as a potential direction of the development of lime Class C fly ash | |
| EP1142622B1 (en) | Method of adsorptive separation of carbon dioxide | |
| CN1012799B (en) | Process for separating nitrogen from mixtures | |
| Wang et al. | Quantifying gel properties of industrial waste-based geopolymers and their application in Pb2+ and Cu2+ removal | |
| CN1311713A (en) | Molecular sieve adsorbent for gas purification and preparation thereof | |
| CN1211468A (en) | Improved binding type zeolite adsorbent, its producing process and its application in non-deep-cooling separation of industrial gas | |
| EA003930B1 (en) | Zeolite adsorbents, method for obtaining them and their use for removing carbonates from a gas stream | |
| CN1385236A (en) | Argon/oxigen selective X-zeolite | |
| Belardi et al. | Crystallization of K–L and K–W zeolites from fly-ash | |
| CA2112796A1 (en) | Magnesium a-zeolite for nitrogen adsorption | |
| US6780806B1 (en) | Lithium-based zeolites containing silver and copper and use thereof for selective absorption | |
| US6878657B2 (en) | Process for the preparation of a molecular sieve adsorbent for the size/shape selective separation of air | |
| CN1214960A (en) | Type A granular lithium zeolite, its preparation process and usage | |
| JP3050147B2 (en) | Adsorbent for air separation, production method thereof and air separation method using the same | |
| CN1868876A (en) | 4A type zeolite molecular sieve and its preparation method | |
| CN1341474A (en) | Temp.-change adsorptive process | |
| CN1116106C (en) | Preparation of activated carbon-zeolite composition with coal gangue | |
| CN1113828A (en) | high efficiency carbon monoxide adsorbent | |
| EP1697284A1 (en) | Regenerative removal of trace carbon monoxide | |
| JP4686889B2 (en) | Method for purifying hydrogen gas | |
| CN113277591B (en) | Preparation method of two-dimensional magadiite/graphene oxide nanosheet composite | |
| WO2000040332A1 (en) | Lithium-based zeolites containing silver and copper and use thereof for selective adsorption | |
| CN1022824C (en) | Preparation method of molecular sieve adsorbent for removing trace krypton and nitrogen oxides in xenon | |
| JPH024442A (en) | High performance lithium adsorbent and its preparation |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |