CN101733070A - X-type zeolite separation material and preparation method thereof - Google Patents
X-type zeolite separation material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of separation materials, particularly discloses an X-type zeolite separation material and a preparation method thereof. The separation material is prepared by modifying sodium X-type aluminosilicate as a basic frame material that is to say, preferred trivalent rare earth positive ions are introduced by a controlled ion exchange method, and univalence Li positive ions can also be introduced in sequence so as to exchange alkali and alkali metal positive ions in the zeolite basically and completely. The surface charge characteristics and the material surface characteristics of the traditional zeolite are improved by introducing the positive ions, and the higher selectivity and the enhanced adsorption characteristic to a specific component to be separated are formed, therefore, the separation material is suitable for non-cryogenic air separation among oxygen-containing mixed gases, oxygen, nitrogen and argon, and can obtain oxygen or argon with high purity more than 99.5 percent.
Description
Technical field
The invention belongs to technical field of separation materials, be specifically related to a kind of oxygen/nitrogen that has concurrently, material of oxygen/argon separating property and preparation method thereof.More particularly, relate to a kind of parting material that is applied to the gas separation field and preparation method thereof, this parting material can be widely used in separating or purify and contains oxygen gas mixture especially oxygen, nitrogen, the argon of constituent of air, especially is fit to obtain purity with non-deep cooling air separating method in air and reaches high-purity oxygen or high purity argon more than 99.5%.
Background technology
Oxygen and argon gas are widely used in various industrial process, air separation technology traditionally mostly is raw material with the air, representational isolation technics can be divided into three big mainstream technologys: Deep Cooling Method (Cryogenic), pressure swing adsorption method (PSA, VSA, VPSA), membrane separation process (Membrane Separation).
By German Ka Erlinde first oxygenerator in the world in invention in 1903, what adopt is exactly Deep Cooling Method, low-temperature distillation process enters industrialization since then, so far this technology remains the mainstream technology in industrial air separation market, in extensive air separation field, have lower separation operating cost and higher oxygen product gas purity (more than 99.5%), but, do not have effective solution for the on-the-spot air feed of specific environments such as the air separation of middle-size and small-sizeization, portable outfit.
The pressure swing adsorption air isolation technics was firstly appeared in early 1960s, and realize suitability for industrialized production the seventies, transformation absorption (Pressure Swing Adsorption is called for short PSA) air separation technology is that the variation by pressure makes the cyclic process that mist adsorbs and desorption hockets in essence in adsorbent, it is a kind of comparatively advanced gas separation, flexible because of it, convenient, small investment, energy consumption is low, the automaticity advantages of higher, pressure swing adsorption was used at the beginning from 1958 and is just developed rapidly, be mainly used in and separate small on-the-spot air feed such as the following production scale of 200TPD, its application practice is mainly reflected in the exploitation of the improvement of technological process and new and effective adsorbent (molecular sieve), be used for producing the common sorbing material that is applicable to from air absorption nitrogen that uses of traditional PSA method of oxygen by air stream, representational sorbing material is such as CaA, CaX, NaX, nitrogen absorbers such as LiX type, related separation principle is based on equilibrium separation in the adsorption system of this sorbing material of this employing, be that sorbing material is stronger than oxygen to the adsorption capacity of nitrogen, it also is selectivity, represent the ratio of adsorbent to the pure component charging equilibrium adsorption capacity of nitrogen and oxygen, usually selectivity reaches more than 3 and can realize the industrial oxygenerating that Energy Efficiency Ratio is pretty good, the selectivity of the synthetic zeolite oxygen nitrogen of improvement can be up to 10, but also in continuous breakthrough, the rational separation process of such selective binding even can accomplish separating fully between nitrogen and oxygen in fact, but, at the argon gas in the constituent of air, adsorption isotherm on these sorbing materials much at one because of oxygen and argon gas, these conventional synthetic zeolites are to oxygen in the raw air and the basic non-selectivity of argon gas, even suppose that all nitrogen are all by zeolite adsorption, in the oxygen enriched product air-flow also because of containing 5% the argon gas of having an appointment, thereby that make to adopt conventional this absorption nitrogen generally can not produce oxygen concentration greater than 95% product gas based on equilibrium adsorption theoretical foundation PSA method, general separation only is limited to 88～95.7% oxygen product, this just limited greatly need purity higher such as cutting, oxygen such as medical treatment are used (need greater than the oxygen 97% or more, even the high-pure gas of needs more than 99.5%).Therefore, obtain higher oxygen purity based on adsorption method, people have to adopt more complicated stage variable pressure adsorption system, domestic patent CN1226142A has just disclosed a kind of pressure swing absorption process that adopts stage variable pressure absorption to obtain purity 98.4%, dispel a large amount of nitrogen with the zeolite nitrogen absorber, to realize the separation of oxygen argon based on the carbon molecular sieve of dynamics stalling characteristic, although realized separation process with single power-equipment, but obviously its oxygen recovery rate of 15% has limited its application greatly, in fact, nitrogen and the argon gas rate of adsorption on CMS (carbon molecular sieve) is roughly the same, so under the situation of air feed, the remainder of oxygen product will contain near 78: 1 nitrogen of its ratio in atmosphere and argon gas, adopt as the ADSIM of ASPEN company transformation absorption simulation softward Simulation result and show, directly adopt CMS as obtaining about 80% maximum oxygen purity on the PSA law theory of adsorbent by air production oxygen, remainder is by with promptly about 19.75% nitrogen of its ratio in atmosphere and 0.25% argon gas, with CMS realize air separation be because sorbing material to the absorption of oxygen than nitrogen result more rapidly, be also referred to as the dynamics selectivity, obviously, viewpoint from oxygen/nitrogen separation, the dynamics selectivity efficient of CMS is starkly lower than the balance selectivity of zeolite, when this will directly cause obtaining oxygen product by air feed with pressure swing absorption process, the not separation of nitrogen that contains significant proportion, this also is that people have to adopt more complicated stage variable pressure adsorption system to realize the reason that high-purity oxygen reclaims, and 88～95.7% oxygen and the argon gas that produce by the PSA oxygen preparation that adopts the nitrogen adsorption agent based on equilibrium adsorption mechanism, the gaseous mixture of nitrogen is as unstripped gas, continuation is isolated more highly purified oxygen with the psa process combination of adopting CMS (carbon molecular sieve), because oxygen and the argon gas equilibrium adsorption capacity on CMS (carbon molecular sieve) also about equally, can only realize that the oxygen argon separates and realize the method for the extraction of high-purity oxygen product with the dynamics selectivity, obviously be limited by the method for designing of the mass-transfer zone of two mechanism inequality, be difficult to accomplish that the coupling of adsorption cycle and CMS (carbon molecular sieve) oxygen argon separating property are limited and be difficult to obtain cost performance piece-rate system preferably;
Stage variable pressure is adsorbed on external representational separation method mainly with US4190424, US4959483, US4913339, US 5395427, US5137549, US4190424, US4959083, US5226933 and US5470378 are representative, the multistage PSA system of existing these technology has adopted two-stage PSA at least, the employing that has nitrogen absorber at first produce oxygen concentration greater than 95.0% product gas by feed air stream, second adsorption bed of forming with carbon molecular sieve is separated argon gas wherein again, the carbon molecular sieve based on the dynamics separation principle that adopts earlier that has obtains poor argon oxygen rich gas again to adopt the nitrogen absorber based on the equilibrium adsorption theory to continue enrichment to produce high-purity oxygen, but in the whole bag of tricks that it adopts, promptly in two sections or multisection type PSA method, have two different mass-transfer zones at least, more typical feature is that at least therein a mass-transfer zone has adopted the carbon molecular sieve of dynamics separation principle to realize separating of oxygen and argon, its systemic circulation complexity, adopted a large amount of surge tanks, power-equipment carries out necessary cleaning for obtaining higher oxygen product, displacement or displacement step, energy resource consumption is huge, cost is high;
Obviously, obtaining to be higher than oxygen separation system more than 95% from constituent of air can the agent of very simple employing nitrogen adsorption obtain based on the pressure swing absorption process of equilibrium adsorption theory, but if will obtain more highly purified oxygen, need to remove the argon gas that initial concentration in the constituent of atomsphere is about 0.934 molar percentage such as the oxygen more than 99.5%, and, preferably can be based on the adsorbent that carries out the transformation sorption cycle under the equilibrium adsorption theory, has certain oxygen argon separating property, U.S. Pat 09782265 has disclosed a kind of X type zeolite with carrying silver AgX that can adsorb argon gas, has the argon oxygen selective, can be applied to the oxygen argon separates, its silver-colored exchange capacity is 20-70%, the Henry's law selectivity ratios of argon/oxygen is 1.15～1.4 in the time of 23 ℃, described zeolite has: under more low-cost than higher silver-colored exchange capacity, compare optionally best of breed of argon with oxygen, this material can be used in the VSA/PSA method of oxygen, theory based on equilibrium adsorption is carried out adsorbing separation, thereby produces purity at the oxygen more than 97%; In addition, U.S. Pat 339872 has disclosed another oxygen selective sorbent that oxygen can be separated from the oxygen-containing gas mixture, this oxygen selective sorbent has higher selectivity, load capacity and absorption rate faster, the load on the matrix of high surface of this adsorbent has a kind of transition elements complex (TEC ' s) of solid form, this transition elements complex is to be spaced from each other equably basically, it comprises a transition elements ion, in the application process of separated oxygen from the oxygen-containing gas mixture, this transition elements ion can be near oxygen flow, said as patent, this adsorbent has greater than about 0.3mmol/g, the oxygen load capacity of (adsorbent), oxygen uptake rate with dividing greater than about 0.3mmol (O2)/g (adsorbent) is applied to the oxygen that the transformation sorption cycle can obtain purity 99%; But these adsorbents generally are difficult to make, and are with high costs, relatively more responsive to the trace impurity in the gas simultaneously, are difficult to industrial applications;
Membrane separation technique is a kind of new and high technology that grows up mid-term in 20th century, industrialization starts from the forties in 20th century, gas membrane Seperation Technology is to utilize the principle of infiltration, it is the direction motion that molecule reduces to chemical potential by film, at first move on the outer surface layer of film, and be dissolved in the film, then in the interior surface layers desorb of the diffusion inside of film to film, its motive force is that this partial pressure of film both sides is poor, because the speed difference the when gas of different component is by film in the mist, thereby reach gas separate reclaim the purpose of purifying gas, in the industrialization practice aspect the oxygen that is applied to purify, be mainly reflected in the research and development of separation membrane and the breakthrough of flow process, up to now, α (Alpha) value that representational its oxygen nitrogen of organic separation membrane that can be applied to air separation separates is mostly between 2～7, the selectivity that the oxygen argon separates mostly is no more than 3.5, α is the selectivity of so-called oxygen nitrogen or oxygen argon, that is to say that separation membrane is to oxygen/nitrogen, the ratio of the infiltration capacity of oxygen/argon, simulation process is calculated and is shown, the separation membrane of oxygen nitrogen separation selectivity about 7 can obtain the oxygen of about 60% following purity, adopt the system of multistage film separation process can obtain purity even greater than 90% oxygen, just disclosed a kind of method and system of from gaseous mixture, isolating a kind of pure component gas as U.S. Pat 626559, can from surrounding air, obtain pure oxygen (purity is 60-90%) effectively, three grades of permeators are provided in the system and method that is provided at least, but not every grade and all need a compressor, although with regard to film separation system, reduced energy requirement, but obviously, produce oxygen relatively with pressure swing absorption process, its separative efficiency is still very low, to such an extent as to can't industrialization use;
Another membrane separation technique production method that solves high-purity oxygen is to adopt an a kind of continuous film tower (CMC) or a continuous film tower are combined with two-stage stripping tower (CMC-TSS) to produce the oxygen of 99% purity, 95% the oxygen that produces with the PSA method is also arranged as raw material, again with membrane separating method purification oxygen, the whole bag of tricks in conjunction with the method purification oxygen purity of continuous film tower (CMC), especially the film circulation piece-rate system with 4 outlet film assemblies is excellent, can the oxygen of production purity more than 99%, energy resource consumption is very high but the extra compression power of this piece-rate system seems, the special membrane separator that the CMC circulation requires is also very expensive, restricted its commercial Application, the selectivity that the oxygen argon separates is no more than its separative efficiency of piece-rate system of 3.5 and also allows the people be difficult to be applied to such as argon gas to purify or the application scenario of collecting oxygen, especially surpass aspect the high-purity oxygen or argon gas 99% or more in purification purity, adopt this hollow-fibre membrane because of the excessive and essentially no industrial applications value of energy resource consumption.
Summary of the invention
In view of above situation, contain the especially efficient separation of oxygen, nitrogen, argon in the constituent of air of oxygen gas mixture in order to solve, the invention provides and a kind ofly can be used for containing the especially parting material of adsorption of oxygen, nitrogen in the air of oxygen gas mixture, and the preparation method of this parting material.
The parting material that the present invention proposes, it is a kind of X type rare earth zeolite of modification, form for the basic skeleton material modification by sodium X type aluminosilicate zeolite, promptly introduce trivalent rare earth cation in certain exchange ratio with higher charge density by the ion-exchange process of being controlled, modification becomes the oxygen sorbing material, also can introduce unit price Li cation in proper order to reach the alkali and the alkali metal cation of replacing substantially fully in the sodium X type aluminosilicate zeolite, modification becomes the nitrogen sorbing material;
The Tricationic of introducing can be IIIB family scandium, yttrium and a lanthanide series rare earth ion in the periodic table, wherein, the preferred a kind of or different kinds of ions wherein of introducing cerium, europium, gadolinium, yttrium, and, exchange step can be that the part exchange also can be all stoichiometric exchange fully, and the exchange ratio can be 10～100%;
The unit price Li cation that order is introduced should reach the alkali and the alkali metal cation of replacing substantially fully in the zeolite, and alkali metal ion content measured should be less than 1% after the exchange of control to make this zeolite;
Above-mentioned parting material is a kind of oxygen selective parting material, have higher oxygen/argon selectivity and higher oxygen load capacity and absorption rate faster, usually, have oxygen/argon selectivity through the material of improveing and reach 12, the oxygen adsorption capacity reaches 0.5mmol/g, and the adsorption time of its 95% oxygen adsorption capacity correspondence is less than 150s;
Above-mentioned parting material is a kind of nitrogen selectivity parting material, have higher oxygen/nitrogen selectivity and higher nitrogen load capacity and absorption rate faster, usually, have oxygen/nitrogen selectivity through the material of improveing and reach 10, the nitrogen adsorption capacity reaches as high as 1.5mmol/g, and the adsorption time of its 95% nitrogen adsorption capacity correspondence is less than 100s;
Above-mentioned zeolitic material is to contain the especially efficient separation of oxygen, nitrogen, argon in the constituent of air of oxygen gas mixture in order to solve, especially at obtaining to surpass more than 97% even 99.5% above high-purity oxygen or high purity argon with the empty technological means of dividing of non-deep cooling, and, this material is based on equilibrium adsorption and non-dynamics absorption to the absorption of nitrogen, oxygen, when being applied to transformation absorption, alternating temperature adsorption process, the mechanism that is based on equilibrium adsorption is carried out separation of transformation sorption cycle or the separation of alternating temperature sorption cycle, and the non-dynamics separation mechanism;
Zeolite of the present invention has been improved the surface charge characteristic and the material surface characteristic of the silicate crystal of traditional zeolite because of introducing cation, is particularly suitable for the empty oxygen that divides of non-deep cooling, argon gas extraction;
But parting material extensive use of the present invention combines with known technology omnibus control system (PSA/VPSA/VSA-O2), from adopting common nitrogen absorber to reclaim purity to dispel argon gas the oxygen of pressure swing adsorption enrichment, the argon mixture gas, perhaps concentrate argon gas and do not change the application scenario of about 93% mole oxygen component that former adsorption system produces substantially up to 99.5% high-purity oxygen;
Parting material of the present invention, the activation powder that can make 0.5～500 μ m are applicable in the fluidization adsorbing separation system in conjunction with a kind of, are applied to the separation process that alternating temperature absorption, transformation absorption or transformation combine with alternating temperature.
The preparation method of X type zeolite separation material provided by the invention is as follows:
1) adopt sodium X type silicon aluminate crystal as the basic framework raw material, this basic framework material can be a sodium X type molecular sieve powder, also can be sodium X type molecular sieve spherical, column, and the chemical expression of this sodium X type silicon aluminate crystal is: Na
86[(AlO
2)
86(SiO
2)
106] .XH
2O, can be easily from most of molecular sieve factory, as the NaX adsorbent of producing by Uop Inc.;
2) above-mentioned sodium X type silicon aluminate crystal is contacted with the aqueous solution of cationic salts to be introduced, carry out the ion-exchange of zeolite;
Above-mentioned ion-exchange, can be earlier and the Tricationic of rare earth element carry out ion-exchange, the modified zeolite of this rare earth ion is rich in formation, this rare earth metal Tricationic is preferably as IIIB family scandium, yttrium and lanthanide series rare earth ion in the periodic table, as a kind of of cerium, europium, gadolinium, yttrium or multiple mixed-cation wherein; Water soluble salt commonly used has acetate, nitrate etc.It also can be all stoichiometric exchange fully that this exchange step can be selected the part exchange, and exchange rate can be 10～100%, and the molar concentration of the aqueous solution of described cationic salts is 0.01～0.1M, preferred 20～90 ℃ of exchange temperature.
The above-mentioned ion-exchange of carrying out also can be proceeded ion-exchange with water soluble salt of ammonia and makes and contain the ammonium ion zeolite, to continue to replace the sodium ion (this exchange step does not influence the Tricationic that has exchanged up on the zeolite basically) that remains on the zeolite; Contain the ammonium zeolite and carry out ion-exchange with lithium salts again and make and contain lithium zeolite or contain lithium and the mixed-cation X zeolite of rare earth, wherein, alkali and alkaline-earth metal ions content is less than 1%, typical lithium salts such as lithium chloride, lithium hydroxide.It also can be that order carries out earlier carrying out after the Tricationic exchange that this ion-exchange step can begin exchange from this step separately.
Each step of above-mentioned exchange is with deionized water washing zeolite, the exchange of per step all can 1 time or repeatedly, 1～30 hour time of contact of each exchange, can be by recording after the analysis meter component analysis, cation can stoichiometry adopt liquid phase adverse current form or solid-state reaction form in the known technology to introduce for 0.1～20 times, preferred exchange cation to be introduced is introduced with the concentration of stoichiometry excessive 10%, and can adopt liquid phase adverse current form or solid-state reaction form in the known technology to carry out, preferably take back the cationic switching method of receipts and carry out.
3) the dry above-mentioned zeolitic material of producing in air or inert atmosphere, preferably dry under vacuum, 20～80 ℃ of baking temperatures.
Can or make particle through the interpolation binding agent through following process activation with the zeolitic material of said process preparation is activated.
Any binding agent, amorphous adhesive or adhesive composition of ion-exchange post crystallization of being applicable to can be used as binding agent, prepared zeolitic material is made ball or make column or make other grain shapes, use as adsorbent, typical binder content is about 10 ~ 20%;
So-called activation is to dispel hydration reaction crystal intercrystalline water, 350～480 ℃ of its activation temperatures, temperature-rise period is the temperature-rise period of control heating rate, and takes certain temperature retention time, typical 1～2 ℃/min of heating rate, for example be warmed up to 100 ℃ ~ 140 ℃, be incubated 1 ~ 2 hour; Continue to be warmed up to 200 ℃ ~ 250 ℃, be incubated 1 ~ 2 hour again; Be warmed up to 350 ℃ ~ 480 ℃ at last, be incubated 2 ~ 6 hours.Preferably in vacuum condition or inert atmosphere, cool off then;
According to above-mentioned preparation method, this separation material can make the particle of 0.5～5mm spherical or (as column) be applied to the separation that pressure-swing absorption process, alternating temperature adsorption process are applied to oxygen-containing mixture with the molecular sieve form.
According to above-mentioned preparation method, this separation material also can be made the activation powder of 0.5～500 μ m, is applicable in the fluidization adsorbing separation system, is applied to the separation process that alternating temperature absorption, transformation absorption or transformation combine with alternating temperature.
According to above-mentioned preparation method, this separation material also can load on the similar porous ceramic support as requested, makes compound organic zeolite membrane parting material, and the method for load comprises the dipping of known technology, coating, spraying, chemical deposition etc.;
Material of the present invention can be widely used in separating or purify and contains especially oxygen, nitrogen or the argon in the constituent of air of oxygen gas mixture, adopt material of the present invention can production purity up to the oxygen more than 99.5%.
The present invention also is fit to combine with known technology omnibus control system (PSA/VPSA/VSA-O2), from adopting common nitrogen absorber to reclaim purity to dispel argon gas the oxygen of pressure swing adsorption enrichment, the argon mixture gas, perhaps concentrate argon gas and do not change the application scenario of about 93% mole oxygen component that former adsorption system produces substantially up to 99.5% high-purity oxygen.
Set forth features more of the present invention below in conjunction with embodiment, the professional and technical personnel will be appreciated that, although reference example of the present invention has carried out partly describing, but this only is an application example of the present invention or a kind of method, all do not violate essence that this patent sets forth other change the category that also belongs to this patent, scope of the present invention is limited by the appending claims scope only.
Description of drawings
Fig. 1 is that the oxygen argon based on equilibrium adsorption mechanism that oxygen selective sorbent is housed separates pressure swing absorption process and device.
Fig. 2 is a two-period form pressure-swing absorption apparatus flow chart, and first section is equipped with nitrogen absorber, and second section is equipped with oxygen selective sorbent, and two sections all based on the pressure swing absorption process of equilibrium adsorption mechanism.
Fig. 3 is equipped with the pressure-swing absorption apparatus of oxygen selective sorbent and the application that combines with common omnibus control system thereof, and two sections all based on the pressure swing absorption process of equilibrium adsorption mechanism.
Fig. 4 is a kind of cyclone separator arrangement that the inoranic membrane parting material is housed.
Number in the figure:
The specific embodiment
The percentage of the said liquid phase exchange of this paper material all is weight percentage.
The percentage of the said gas of this paper is percent by volume.
The said pressure of this paper all refers to absolute pressure.
The selectivity of the said absorption of this paper is defined as it as the selectivity of nitrogen oxygen:
α (Alpha) value, the selectivity of nitrogen oxygen=(X N2/Y N2)/(X O2/Y O2)
X N2 and X O2 are respectively the molar fraction of nitrogen and oxygen in the absorption mutually in the formula, and Y N2 and Y O2 are respectively the molar fraction of nitrogen and oxygen in the gas phase, and same, the selectivity of oxygen argon is as follows:
α (Alpha) value, the selectivity of oxygen argon=(X O2/Y O2)/(X Ar/Y Ar)
X O2 and X Ar are respectively the molar fraction of oxygen and argon gas in the absorption mutually in the formula, and Y O2 and Y Ar are respectively the molar fraction of oxygen and argon gas in the gas phase
Adsorbent can be analogized according to above-mentioned expression formula other component selectivity;
For obtain a kind of excellent performance at containing especially constituent of air oxygen of oxygen gas mixture, nitrogen, the parting material that is applicable to the empty branch application of non-deep cooling between the argon, the present invention is the basic skeleton material with the low this traditional silicate crystal of silicon zeolite of NaX, by a series of ion-exchange process of being controlled, the trivalent rare earth cation that preferential by a certain percentage introducing preferably has higher charge density, also can introduce unit price Li cation in proper order to reach the alkali and the alkali metal cation of replacing substantially fully in the zeolite, introduce cation according to the method and improved the surface charge characteristic and the material surface characteristic of the silicate crystal of traditional zeolite, make material show the physical absorption of specific components and reversible catalysis characterization of adsorption at gas component, to such an extent as to formed the characterization of adsorption for the treatment of higher selectivity of separation of specific components and reinforcement, thereby make material have to containing especially constituent of air oxygen of oxygen gas mixture, nitrogen, the non-deep cooling sky that is applicable between the argon is divided into possibility, in addition, because of the trivalent rare earth cation of introducing has improved the competitive adsorption characteristic of material at sensitive ingredients such as moisture common in the constituent of air, relatively have lower hydrophilic characteristics and have better heat endurance with the LiX zeolite that exchanges fully usually;
It is better in the separating property between the oxygen in the self-contained oxygen gas mixture of the empty branch technological means of non-deep cooling especially constituent of air, nitrogen, the argon that these above features make that the material with the present invention's preparation has, that is, higher adsorption capacity, higher selectivity and the adsorption time of 95% saturated adsorption capacity correspondence faster.
Embodiment 1
Get NaX molecular sieve activation powder 100g, 80 ℃ of following conditions with the cerium acetate solution 4L contact of 25mmol/L 4 times, each 1 hour.
Each contact back is filtered described hot solution and is spent deionised water till described eluate does not have acetic acid ion.
In the down dry nitrogen of room temperature (25 ℃), make then and contain the cerium cation exchange rate and reach 85% rare earth X type zeolite.
With the heating rate of 1.5 ℃ of per minutes, under the vacuum condition of 100Pa, sample progressively is warmed up to 120 ℃, 200 ℃ and respectively is incubated 2 hours, at last be warmed up to 380 ℃ and be incubated 4 hours with this activating zeolite with the heating rate of 1.5 ℃ of per minutes.
Before taking out, make it to be cooled to room temperature, cool off in the drying box of afterwards this material transfer to drying nitrogen being protected to prevent to adsorb once more moisture content.
Adopt gravimetry to measure nitrogen (N
2), argon gas (Ar) and oxygen (O
2) pure component adsorption isotherm on above-mentioned rare earth X zeolite sample, under 15 ℃ and 760mmHg pressure, oxygen adsorbance 0.3mmol/g, oxygen is 12.0 to the selectivity of argon, oxygen is 1.8 to the selectivity of nitrogen
Test result shows that this rare earth X type zeolite is a kind of good oxygen argon parting material.
Embodiment 2
Make by embodiment 1 and to contain the cerium cation exchange rate and reach 20% rare earth X type zeolite, continue to remain cation exchange and become NH4-rare earth X type zeolite with conventional switching method.
The ammonium sulfate of at least 2 times of equivalents is that 80 ℃ contact 2 hours down, introducing a spot of ammonia spirit again, to adjust the pH value of ammonium sulfate be 8.5 to avoid the damage of ion-exchange to material structure, filtration is washed with deionized water, repeat 4 times, be no more than 0.01 equivalent until the residual alkali metal ion and make NH4-rare earth X type zeolite.
Under 50 ℃ LiOH, the deionized water of stoichiometry excessive 10% are sized mixing, agitation as appropriate with the compressed air aeration about 10 hours, is finished that the exchange back is filtered and is that 9 LiOH solution drip washing makes Li-rare earth X type zeolite with pH value.
Zeolite with the said process preparation can be activated through following process activation or through adding the binding agent balling-up again, heating rate with 2 ℃ of per minutes, under the vacuum condition of 100Pa, sample progressively is warmed up to 120 ℃, 200 ℃ and respectively is incubated 2 hours, at last be warmed up to 360 ℃ and be incubated 4 hours this activating zeolite with the heating rate of 2 ℃ of per minutes.
Before taking out, make it to be cooled to room temperature, cool off in the drying box of afterwards this material transfer to drying nitrogen being protected to prevent to adsorb once more moisture content.
Adopt gravimetry to measure nitrogen (N2), argon gas (Ar) and the pure component adsorption isotherm of oxygen (O2) on above-mentioned rare earth X zeolite sample, under 15 ℃ and 760mmHg pressure, nitrogen adsorbance 1.2mmol/g, nitrogen is 10.0 to the selectivity of oxygen, argon is 1.15 to the selectivity of oxygen
Test result shows that this Li-rare earth X type zeolite is a kind of good nitrogen absorber.
Get the cerium cation exchange rate that contains that embodiment 1 makes and reach 85% rare earth X type zeolite, dry down in room temperature (25 ℃);
Press known technology and add the binding agent balling-up, the particle between screening 1.0～1.5mm;
In the vacuum baking stove with the heating rate of 1.5 ℃ of per minutes, under the vacuum condition of 100Pa, sample progressively is warmed up to 120 ℃, 200 ℃ and respectively is incubated 2 hours, at last be warmed up to 380 ℃ and be incubated 4 hours this activating zeolite with the heating rate of 1.5 ℃ of per minutes;
Before taking out, make it to be cooled to room temperature, cool off in the drying box of afterwards this material transfer to drying nitrogen being protected to prevent to adsorb once more moisture content;
Can use typical pressure swing absorption process with the parting material that said method is produced, as the PSA/VPSA/VSA variable-pressure adsorption separating method, according to the technological process shown in the accompanying drawing 1, adsorbent is installed in the 01A shown in the accompanying drawing 1, in the 01B adsorption tower, the gaseous mixture of the oxygen with 95% and about argon gas of about 5% is a raw material, adopts the oxygen of pressure-swing absorption process acquisition more than 99.5% based on equilibrium adsorption mechanism;
Usually, the nitrogen adsorption agent comprises as CaA, CaX, and NaX, the nitrogen absorber that known technologies such as LiX type are made can simply obtain 95% the oxygen and the gaseous mixture of about argon gas of about 5% with pressure swing absorption process.
Embodiment 4
Preferred embodiment 2 makes contains Li-rare earth X type activating zeolite zeolite granular, it has the granularity between 1.0～1.5mm, is installed in the 101A in first section pressure swing adsorption technique flow process shown in the accompanying drawing 2, in the 101B adsorption tower, device is raw material with the air, can obtain about 96% oxygen;
The cerium cation exchange rate that contains with embodiment 1 system reaches 85% rare earth X type activating zeolite zeolite granular again, it has the granularity between 1.0～1.5mm, be installed in the 201A in second section pressure swing adsorption technique flow process shown in the accompanying drawing 2, in the 201B adsorption tower, device preceding stage product is a raw material, can obtain about 99.9% oxygen;
The parting material of producing with said method adopts the technological process shown in the accompanying drawing 2 can directly produce the oxygen of purity 99.9% in air, this two-part variable-pressure adsorption separating method, with the air is raw material, and the mass transfer of two sections transformations absorption is all based on the PSA/VPSA/VSA variable-pressure adsorption separating method of equilibrium adsorption mechanism.
Embodiment 5
The cerium cation exchange rate that contains with embodiment 1 system reaches 85% rare earth X type activating zeolite zeolite granular, and it has the granularity between 1.0～1.5mm;
At first obtaining the about oxygen more than 93% of about purity with known technology VPSA/VSA variable-pressure adsorption separating method is unstripped gas, the parting material of producing with said method is used typical pressure swing absorption process again, from this oxygen, dispel argon gas in the argon mixture gas and reclaim purity up to 99.5% high-purity oxygen or concentrated argon gas, and the oxygen that does not change about 93% mole oxygen component of former gaseous mixture generation substantially influences the application of original system, this point, it obviously is useful producing about 93% oxygen and need the application scenario of 99.5% above oxygen at the empty branch of existing fairly large non-deep cooling, accompanying drawing 3 has illustrated this application, among the figure, after about 93% the unstripped gas that is produced by the known technology pressure swing adsorption oxygen making device enters system, be mounted the pressure-swing absorption apparatus of aerobic gas adsorbent, 01A wherein, the cerium cation exchange rate that contains that 01B is equipped with embodiment 1 system reaches 85% rare earth X type activating zeolite zeolite granular, gas is divided into 2 strands of air-flows after device separates, a kind of is that purity is greater than the high-purity oxygen more than 99.5%, the back is mixed as another kind of oxygen rich gas output than low-purity in another oxygen depleted exhaust air output back with unstripped gas, purity about 90～94%, because of carrying out simple designs and adjusting to flow system flow, the flow that the pressure-swing absorption apparatus of this oxygen adsorbent has been installed in employing can control to the scope that reduces unstripped gas purity slightly, substantially do not change stock blend, continue to use thereby make original gas not influence, this is fit to have the application scenario of empty branch of extensive non-deep cooling and needs high-purity oxygen product very much.
Choosing porous ceramics is supporter, the cerium cation exchange rate that contains with embodiment 1 system reaches 85% rare earth X type zeolite dipping, the spraying or with the method for vapour deposition porous ceramic support is adhered to one deck thin layer sorbing material and makes tubulose, the parting material of doughnut boundling form or chemical-process exchange plate-like form, promptly become the organic zeolite membrane material after the activation, can be applicable to the special Dynamic Membrane separation process of optimizing, the simple separation that realizes oxygen/argon, the section of structure of a typical inoranic membrane separator as shown in Figure 4,1 is remained gas collection mouth, 2 is separator shell, 3 is the unstripped gas inlet channel, 4 is oxygen argon separation membrane material, 5 is the remained gas collection channel, 6 are infiltration gas collection mouth, 7 are the unstripped gas inlet, wherein, 4 can be tubulose, the various installation forms of the parting material of doughnut boundling form or chemical-process exchange plate-like form;
Combine with 95% the oxygen that common transformation adsorbing separation oxygen preparation makes, can obtain the high-purity oxygen of purity 99.7%;
The omnibus control system that makes up with the molecular screen material of embodiment 2 preparations combines, and can obtain the high-purity oxygen of purity 99.9%.
Embodiment 7
The cerium cation exchange rate that contains with embodiment 1 system reaches 85% rare earth X type activating zeolite powder, its granularity is between 1.0～10 μ m, can be applicable to adsorption separation process through the fluidization TSA of special optimization, utilize low-grade heat energy from waste gas to produce oxygen enrichment, this obviously is useful for the application scenario that a large amount of oxygen of needs carry out oxygen-enriched combusting, compare with general transformation absorption, because this adsorbing separation system oxygen mode only consumes the energy that absorbent particles is carried in fluidization, and a large amount of gas compression that does not consume common omnibus control system needs can, thereby make system oxygen have extremely low energy resource consumption, being converted to the energy resource consumption of extracting every cube 100% pure oxygen is approximately below the 0.04KW, this is that other separation method is unapproachable, a typical TSA operating procedure parameter that adopts this parting material to carry out is 185 ℃ of hot sides, 30 ℃ of cold sides, in this piece-rate system, absorbent particles is in the fluidization recurrent state always, and comprise pneumatic transport equipment circulation transportation through powder conveying equipment, can be adsorbed with the low temperature side oxygen in the powder separation equipment of gas phase exchange, can oxygen discharged with the high temperature side in the powder separation equipment of gas phase exchange, the heat of high temperature side provides can be from any type of heater, preferably the low-grade heat energy from waste gas from kiln carries out heat exchange, the low-temperature receiver of low temperature side can be from any type of refrigeration plant, preferably from the energy-saving machinery of air source heat pump and so on, by above-mentioned, the professional and technical personnel can directly extract 25～99% oxygen supply burning easily in air with this piece-rate system, and this separation can be multistage in parallel or series connection.
In method described above or shown in the drawings, technological parameter or the device, can make various changes and can not deviate from scope of the present invention.Therefore, though this method is preferred use be the switching method, time of contact, temperature of the preferred exchange cation of any requirement and exchange cation and prepare suitable features such as material in conjunction with the application technology principle, for convenience just shown in the drawings or explain in above concrete property of the present invention, because according to the present invention, these characteristics also can combine with other characteristic.Those skilled in the art can admit that improvement that other the method without prejudice to this patent spirit, device or combination are used and the embodiment that can adopt also should comprise within the scope of the appended claims in practice of the present invention.
Claims (7)
1. an X type zeolite separation material is characterized in that it being to produce acquisition by sodium X type silicon aluminate crystal through improvement, and its improvement steps is as follows:
1) adopt sodium X type silicon aluminate crystal as the basic framework raw material, the chemical expression of this sodium X type silicon aluminate crystal is: Na
86[(AlO
2)
86(SiO
2)
106] XH
2O;
2) above-mentioned sodium X type silicon aluminate crystal is contacted with the aqueous solution of cationic salts to be introduced, carry out the ion-exchange of zeolite; Wherein:
Tricationic with rare earth element carries out ion-exchange earlier, obtain the oxygen sorbing material, this exchange step is selected part exchange or all stoichiometric exchange fully, exchange rate is 10～100%, the molar concentration of the aqueous solution of described cationic salts is 0.01～0.1M, and the exchange temperature is 20～90 ℃;
Proceed ion-exchange with water soluble salt of ammonia then, make and contain the ammonium ion zeolite to continue to replace the sodium ion that remains on the zeolite, contain the ammonium zeolite and carry out ion-exchange with lithium salts again, make and contain lithium zeolite or contain lithium and the mixed-cation zeolites of rare earth, obtain the nitrogen sorbing material; Wherein alkali metal ion content measured is less than 1%;
Each step of above-mentioned exchange is with deionized water washing zeolite, and per step is exchanged for 1 time or repeatedly, each 1～30 hour time of contact;
It is 3) above-mentioned that to carry out the zeolite that ion-exchange finishes dry in air or inert atmosphere.
2. X type zeolite separation material according to claim 1 is characterized in that described rare earth element is IIIB family scandium, yttrium and lanthanide series.
3. X type zeolite separation material according to claim 2 is characterized in that described rare earth element is a kind of of cerium, europium, gadolinium, yttrium, perhaps wherein several.
4. the preparation method of an X type zeolite separation material is characterized in that concrete steps are as follows:
1) adopt sodium X type silicon aluminate crystal as the basic framework raw material, the chemical expression of this sodium X type silicon aluminate crystal is: Na
86[(AlO
2)
86(SiO
2)
106] XH
2O;
2) above-mentioned sodium X type silicon aluminate crystal is contacted with the aqueous solution of cationic salts to be introduced, carry out the ion-exchange of zeolite; Wherein:
Tricationic with rare earth element carries out ion-exchange earlier, obtain the oxygen sorbing material, this exchange step is selected part exchange or all stoichiometric exchange fully, exchange rate is 10～100%, the molar concentration of the aqueous solution of described cationic salts is 0.01～0.1M, and the exchange temperature is 20～90 ℃;
Proceed ion-exchange with water soluble salt of ammonia then, make and contain the ammonium ion zeolite to continue to replace the sodium ion that remains on the zeolite, contain the ammonium zeolite and carry out ion-exchange with lithium salts again, make and contain lithium zeolite or contain lithium and the mixed-cation zeolites of rare earth, obtain the nitrogen sorbing material; Wherein alkali metal ion content measured is less than 1%;
Each step of above-mentioned exchange is with deionized water washing zeolite, and per step is exchanged for 1 time or repeatedly, each 1～30 hour time of contact;
It is 3) above-mentioned that to carry out the zeolite that ion-exchange finishes dry in air or inert atmosphere.
5. preparation method according to claim 4 is characterized in that prepared parting material carries out further activation processing, carries out activation processing after perhaps making particle with binding agent; Its activation temperature is 350 ~ 480 ℃, and soak time is 2 ~ 10 hours, and the heating rate that is warmed up to activation temperature is 1 ~ 2 ℃/min; In vacuum condition or inert atmosphere, cool off then.
6. preparation method according to claim 4 is characterized in that described rare earth element is IIIB family scandium, yttrium and lanthanide series.
7. preparation method according to claim 6 is characterized in that described rare earth element is a kind of of cerium, europium, gadolinium, yttrium, perhaps wherein several.
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| CN109289764B (en) * | 2018-11-02 | 2021-04-06 | 太原理工大学 | Synthesis method of TUT-5A and application thereof in efficient separation of propyne propylene |
| CN109289764A (en) * | 2018-11-02 | 2019-02-01 | 太原理工大学 | The synthetic method of TUT-5A a kind of and its application in propine propylene efficiently separates |
| CN110152715A (en) * | 2019-05-28 | 2019-08-23 | 内江师范学院 | Fe-X type core-shell structure molecular sieve catalyst and its preparation method and application |
| CN114618438A (en) * | 2020-12-10 | 2022-06-14 | 中国科学院大连化学物理研究所 | Oxygen selective adsorbent and preparation method and application thereof |
| CN114618438B (en) * | 2020-12-10 | 2023-06-06 | 中国科学院大连化学物理研究所 | Oxygen selective adsorbent and preparation method and application thereof |
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Application publication date: 20100616 |