CN100497174C - Synthesis of zeolite molecular sieves - Google Patents
Synthesis of zeolite molecular sieves Download PDFInfo
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- CN100497174C CN100497174C CNB2005100647559A CN200510064755A CN100497174C CN 100497174 C CN100497174 C CN 100497174C CN B2005100647559 A CNB2005100647559 A CN B2005100647559A CN 200510064755 A CN200510064755 A CN 200510064755A CN 100497174 C CN100497174 C CN 100497174C
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Abstract
Synthesis of zeolite molecular sieve is carried out by preparing a material for synthesizing zeolite molecular sieve, gluing, crystallizing, filtering to obtain zeolite molecular sieve, reacting the filtered mother liquid with aluminum-containing compound, gluing, filtering to obtain gel, and contacting industrial waste solution containing ammonia and nitrogen with the obtained gel. It can be used as zeolite molecular sieve raw materials.
Description
Technical field
The present invention relates to a kind of synthesis of zeolite molecular sieves, more specifically to the low synthesis of zeolite molecular sieves of a kind of ammonia nitrogen quantity discharged.
Background technology
The chemical that contains ammonia nitrogen because of its good water-solubility with characteristics such as be easy to remove, is widely used in catalystic material and Preparation of catalysts.Contain the use of the chemical of ammonia nitrogen in a large number, make and contain a large amount of ammonia nitrogen materials in the processing wastewater that discharges in the production process.With the ammonium exchange of zeolite molecular sieve and the washing after the exchange is example, and the ammonia-nitrogen content in the filtered liquid of ammonium exchange is generally 4000-10000 μ g/g; Ammonia-nitrogen content in the washing water is generally 150-1500 μ g/g.Too high ammonia-nitrogen content in the trade effluent causes the serious environmental problem that turns to feature with water eutrophication easily.
Although multiple ammonia nitrogen processing method is arranged, can be used for reducing or eliminate the influence of ammonia nitrogen environment as blow-off method, membrane separation process and biological removal of nitrogen method.But exploitation ammonia nitrogen discharging production technology low or that can be recycled should be fundamentally to eliminate and reduce the more economic and suitable technology of ammonia nitrogen to the environment disadvantageous effect.
Summary of the invention
The objective of the invention is provides a kind of new low synthesis of zeolite molecular sieves of ammonia nitrogen quantity discharged on the basis of existing zeolite molecular sieve synthetic technology.
Method provided by the invention may further comprise the steps: the material of a kind of synthesis zeolite of (1) preparation, one-tenth glue, crystallization are also filtered, and obtain zeolite molecular sieve; (2) step (1) is filtered the mother liquor and at least a aluminum contained compound that obtain and be reacted into glue and filtration, obtain gel; (3) industrial wastewater that will contain ammonia nitrogen contacts with the gel that step (2) obtains.
Adopt method provided by the invention, when obtaining the zeolite molecular sieve product, the ammonia-nitrogen content in the trade effluent is obviously reduced.For example, adopt the synthetic y-type zeolite molecular sieve of the inventive method, handling a kind of ammonia-nitrogen content simultaneously is the industrial wastewater that contains ammonia nitrogen that is derived from zeolite molecular sieve ammonium ion exchange, washing of 1500 μ g/g, and the ammonia nitrogen in the draining can be to 30 μ g/g.
In addition, the gel that contains ammonia nitrogen can be used as the synthesis zeolite raw material and further utilizes.Ammonia nitrogen wherein is after the crystallization of zeolite molecular sieve finishes, carry absorbing through gas and turn to ammonium salt or ammonium salt aqueous solution with acid, the ammonium ion exchange process that its circulation can be used for zeolite molecular sieve, thus realize containing the ammonia nitrogen chemical in the synthesis zeolite process recycle.
Description of drawings
Fig. 1 contains the schematic flow sheet of the synthesis zeolite method of ammonia nitrogen gel for synchronous recovery provided by the invention.
Fig. 2 is the schematic flow sheet of the synthesis zeolite method of synchronous recovery ammonia provided by the invention.
Embodiment
According to method provided by the invention, wherein said zeolite molecular sieve can be any one known zeolite molecular sieve.For example, faujusite, beta, mordenite, ZSM series boil (as ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35 and ZSM-38).The material of described synthesis zeolite, one-tenth glue, crystallization condition, different different because of this class of synthesis zeolite, its preparation and operational condition are well known in the art, do not give unnecessary details here.
Described mother liquor and described aluminum contained compound are reacted into glue and filter and can adopt any one existing method to carry out.For example, the disclosed NaY sieve synthesis procedure of US4164551 reclaims the method for silicon in the mother liquor.
Described aluminum contained compound is preferably and contains aluminium salt, as in Tai-Ace S 150, sodium metaaluminate, aluminum nitrate, the aluminum chloride one or more.Look different situations, these aluminum contained compounds comprise their aqueous solution.The consumption of preferred aluminum contained compound is reacted into glue and filtering condition and makes the chemical constitution of the gel that finally obtains be: rNa
2O:Al
2O
3: xSiO
2: yX:zH
2O, wherein X is acidic oxide and/or element, r=0.001-2, x=3-11, y=0.05-5, z=100-500.More preferably make the chemical constitution of the gel that finally obtains be: rNa
2O:Al
2O
3: xSiO
2: yX:zH
2O, wherein X is sulfur oxide such as sulphur trioxide, r=0.05-1.5, x=7-10, y=0.1-2.5, z=200-400.
According to method provided by the invention, preferred described step (2) comprises an aged step after becoming glue and before filtering.Described aging condition is the normal condition of synthetic amorphous silicon oxide-aluminum oxide, and for example, aging temperature is 20-95 ℃, and the time is 0.5-2 hour.
According to method provided by the invention, embodiment preferred is under the condition of being adsorbed by described gel of the ammonia nitrogen in being enough to make the industrial wastewater that contains ammonia nitrogen, and the described industrial wastewater that contains ammonia nitrogen that is derived from zeolite molecular sieve ammonium ion exchange, washing is contacted with described gel.For example, by described waste water solution and described gel are pulled an oar jointly, filtering method; Or with the method for described waste water solution by an adsorption bed absorption that constitutes by described gel.When adopting described methods of beating to carry out, the amount that can determine described waste water and gel according to the ammonia loading capacity and the emission standard of ammonia nitrogen content, gel in the described waste water solution; When the method that adopts the adsorption bed absorption that is made of gel is carried out, can detect ammonia nitrogen content in the adsorption liquid by online, with the period of a permutation of definite sorbent material gel or the treatment capacity of described waste water solution.Preferred operational condition should make the ammonia-nitrogen content that finally contains in the ammonia nitrogen industrial wastewater reduce to less than 30 μ g/g.The ammonia-nitrogen content that finally contains in the ammonia nitrogen industrial wastewater is reduced to less than 15 μ g/g.
According to method provided by the invention, the described gel that contains ammonia nitrogen can all or part of raw material as synthesis zeolite, is about to the step (1) that its raw material as silicon, aluminium returns described method and uses.
According to method provided by the invention, when the material of synthesis zeolite is all or part of is when containing the gel of ammonia nitrogen, to preferably including the step that a gas is put forward with filtration slurries before after the described crystallization, to remove ammonia wherein, described gas extracting method is the conventional gas blowing method, and gas is carried and can be carried out at crystallization jar or middle the commentaries on classics in the batch can.Described gas is preferably air and/or water vapour, described gas is carried comprising that gas flow, gas carries the time without limits, preferably make ammonia-nitrogen content in the draining behind the described dope filtration less than 100 μ g/g, further, more be preferably less than 15 μ g/g preferably less than 30 μ g/g.
Contain ammonia in the discharging gas that described gas is carried, therefore, according to method provided by the invention, preferably include the step that an ammonia reclaims, described ammonia recovery method is well known in the art, for example the method that this gas is contacted with acid.Described acid is preferably mineral acid, as in sulfuric acid, nitric acid and the hydrochloric acid one or more, more preferably inorganic acid concentration is 5-50% dilute acid solution.
Method provided by the invention can realize by flow process shown in Figure 1.
Wherein, prepare the synthesis zeolite material according to ordinary method, become glue, crystallization, filtration, zeolite molecular sieve after the filtration reclaims as product, mother liquor becomes glue, aging (or aging), filtration with the reactant aqueous solution of aluminum contained compound or aluminum contained compound, filtered liquid wherein is as the discharging of purifying waste water that has reduced silicone content, and the gained filter cake mixes making beating, filters with the industrial wastewater that contains ammonia nitrogen; Or the industrial wastewater that directly will contain ammonia nitrogen is as the washing fluid flush cake, filtered liquid or wash back liquid as the discharging of purifying waste water that has reduced ammonia-nitrogen content, and the gel that contains ammonia nitrogen reclaims as product.
Method provided by the invention can realize by flow process shown in Figure 2.
Be with the difference of flow process shown in Figure 1, this flow process will contain the prepared using of the gel of ammonia nitrogen as synthesis zeolite, and after crystallization and before filtering slurries are carried out gas and carry, to remove ammonia nitrogen wherein, the ammonia gas that contains after gas is carried contacts with the aqueous solution that contains acid substance such as diluted acid with acid, to reclaim ammonia wherein.
Ammonia in containing ammonia gas is converted into rare ammonium salt solution with after dilute acid solution contacts, and this ammonium salt solution can be directly used in the ammonium ion exchange process of follow-up zeolite molecular sieve.
Synthesis of zeolite molecular sieves provided by the invention is applicable to all synthesizing with the zeolite molecular sieve siliceous, that aluminum compound is raw material.For example, common faujusite, beta, mordenite, ZSM series are boiled synthesizing of (as ZSM-5, ZSM-11, ZSM-12, ZSM-23, ZSM-35 and ZSM-38).
To the present invention be described by example below.
Embodiment 1
By the synthetic NaY zeolite molecular sieve of flow process shown in Figure 1, method according to the embodiment 4 of patent CN96114271 is synthetic, obtains 2.2 liters in 470 gram Y zeolite molecular sieves 1, mother liquor after filtration, and the physico-chemical property of Y1 sees Table 1, the silicone content of measuring in the mother liquor is 55 grams per liters, modulus (SiO
2/ Na
2The O mol ratio is 1.78).Take by weighing Tai-Ace S 150 [molecular formula Al
2(SO
4)
318H
2O] 192 gram preparation aluminium content (in aluminum oxide) are the aqueous solution of 90 grams per liters, this solution is joined one 5 liters becoming in the glue jar with mother liquor L1 simultaneously in the mode that also flows, regulate the flow of aluminum sulfate aqueous solution, making into glue pH value is 9, becoming the temperature of glue process is 30 ℃, and the slurries that become glue to generate are collected in a digestion tank.Wore out 2 hours at 30 ℃ then, suction strainer obtains gel 1850 grams, and it consists of 2.06Na
2O:Al
2O
3: 9SiO
2: 2.0SO
3: 366H
2O.Under the suction strainer condition, with the filter cake after filtering is that the adsorption bed ammonia nitrogen concentration is 20 liters of these filter cakes of drip washing of liquid after a kind of filter that is derived from after the zeolite molecular sieve ammonium exchanges of 1500 μ g/g, ammonia-nitrogen content in the solution after the analysis drip washing, its value is 20 μ g/g, continued to blot 10 minutes, obtain containing the gel of ammonia nitrogen, it consists of 0.006Na
2O:4.00NH
3: Al
2O
3: 7.8SiO
2: 0.95SO
3: 323H
2O, its solid content are 7.8%, Al
2O
3Content is 15.8%.
By the synthetic NaY zeolite molecular sieve of flow process shown in Figure 2,209 kilograms of ammonium type alumino silica gel raw materials that embodiment 1 is obtained and water glass 153 liters (Shandong catalyst plant, SiO
2Content 252 grams per liters, modulus 3.29), 38 liters (the directed agents prescription adopts 16Na to directed agents
2O:Al
2O
3: 15SiO
2: 320H
2O, directed agents be prepared as 22.6 premium on currency glass and 15.4 liters of sodium aluminate solutions (Shandong catalyst plant, Na
2O content 296 grams per liters, Al
2O
3Content 42 grams per liters) mix to stir after 1 hour, 30 ℃ aging 12 hours down), 41.1 liters of Shandong catalyst plants of alum liquor, Al
2O
3Content 90 grams per liters), sodium aluminate solution 55 liters of (Shandong catalyst plant, Al
2O
3Content 108 grams per liters, Na
2O content 156 grams per liters) mix.Obtain the material of synthesis zeolite, it consists of 2.6Na
2O:Al
2O
3: 7.4SiO
2: 180H
2O.Crystallization process carries out in reactor, temperature is controlled at 90-97 ℃, and crystallization 24 hours changes the slurries after the crystallization over to gas and carries jar, at the bottom of carrying jar, gas is equipped with gas distributor, by this gas distributor, feed pressurized air gas and carry 2 hours, gas flow is 1.5 liters/minute, dope filtration obtains 450 liters in y-type zeolite molecular sieve Y2, mother liquor afterwards, the physico-chemical property of Y2 sees Table 1, and the silicone content of mother liquor L2 is 40 grams per liters, Na
2O content is 23 grams per liters, and ammonia-nitrogen content is 12 μ/g.It is that 30% dilution heat of sulfuric acid absorbs that gas stripping gas adopts concentration, obtains concentration and be 10% ammoniumsulphate soln.
Take by weighing 28.5 kilograms in Tai-Ace S 150 (with example 1), preparation aluminium content (in aluminum oxide) is the aluminum sulfate aqueous solution of 90 grams per liters, this solution is joined one 1 cubical with L2 simultaneously in the mode that also flows to be become in the glue jar, regulate the flow of aluminum sulfate aqueous solution, making into glue pH value is 10, becoming the temperature of glue process is 80 ℃, and the slurries that become glue to generate are collected in a digestion tank.Then in 80 ℃ aging 2 hours, suction strainer obtains 256 kilograms of gels, it consists of 2.0Na
2O:Al
2O
3: 6.5SiO
2: 2.2SO
3: 350H
2O.Under the suction strainer condition, with the filter cake after filtering is that the adsorption bed ammonia nitrogen concentration is 1.4 cubes of these filter cakes of drip washing of liquid after a kind of filter that is derived from after the zeolite molecular sieve ammonium exchanges of 3000 μ g/g, ammonia-nitrogen content in the solution after the analysis drip washing, its value is 25 μ g/g, continued to blot 10 minutes, obtain containing the gel of ammonia nitrogen, it consists of 0.004Na
2O:4.40NH
3: Al
2O
3: 6.5SiO
2: 1.05SO
3.405H
2O.
Embodiment 3
By the synthetic ZSM-5 zeolite molecular sieve of flow process shown in Figure 1, method according to the embodiment 1 of patent CN85100463 is synthetic, obtain 100 gram zeolite molecular sieve Z1 after filtration, mother liquor L3,759 milliliters, the physico-chemical property of Z1 sees Table 1, and the silicone content of measuring among the mother liquor L3 is 20 grams per liters, modulus is 1.80, takes by weighing Tai-Ace S 150 [molecular formula Al
2(SO
4)
318H
2O] gram preparation aluminium content (in aluminum oxide) is the aqueous solution of 90 grams per liters, this solution is joined one 2 liters becoming in the glue jar with mother liquor L3 simultaneously in the mode that also flows, regulate the flow of aluminum sulfate aqueous solution, making into glue pH value is 11, becoming the temperature of glue process is 25 ℃, and the slurries that become glue to generate are collected in a digestion tank.Suction strainer obtains gel 154 grams, and it consists of 2.8Na
2O:Al
2O
3: 10SiO
2: 1.8SO
3: 345H
2O.Under the suction strainer condition, with the filter cake after filtering is that the adsorption bed ammonia nitrogen concentration is 900 milliliters of these filter cakes of drip washing of liquid after a kind of filter that is derived from after the zeolite molecular sieve ammonium exchanges of 1500 μ g/g, ammonia-nitrogen content in the solution after the analysis drip washing is 25 μ g/g, continued to blot 10 minutes, obtain containing the gel of ammonia nitrogen, it consists of 0.01Na
2O:3.85NH
3: Al
2O
3: 9.6SiO
2: 0.90SO
3: 315H
2O.
Embodiment 4
By the synthetic ZSM-5 zeolite molecular sieve of flow process shown in Figure 2, the ammonia nitrogen alumino silica gel 154 that contains that takes by weighing embodiment 3 restrains (solid content is 8.0%, and wherein aluminum oxide 14.5%, silicon oxide 81.9%, ammonia nitrogen 11.0%), adds 211.9 milliliters of water glass solutions, and its concentration is SiO
2: 250 grams per liters, modulus 3.2 is taken from the Shandong catalyst plant, adds NaY molecular sieve 1.5 gram (SiO
2/ Al
2O
3=5.0, solid content 80%), add 216 milliliters of the sulphuric acid solns that concentration is 3.0M.After stirring, in an autoclave, be warming up to 180 ℃ of crystallization 16 hours, change gas over to after being cooled to the slurries after the crystallization below 100 ℃ and carry jar, at the bottom of carrying jar, gas is equipped with gas distributor, by this gas distributor, feed pressurized air gas and carry 1 hour, gas flow is 1.0 liters/hour, dope filtration obtains ZSM-5 type zeolite molecular sieve Z2, mother liquor L4500 milliliter afterwards, the physico-chemical property of Z2 sees Table 1, and the pH value of mother liquor L4 is 11, and ammonia-nitrogen content is 5 μ g/g, the silicone content of measuring wherein is 25 grams per liters, modulus 2.3.It is that 30% dilution heat of sulfuric acid absorbs that gas stripping gas adopts concentration, obtains concentration and be 5% ammoniumsulphate soln.
Take by weighing Tai-Ace S 150 (with example 1) 15.4 grams, preparation aluminium content (in aluminum oxide) is the aluminum sulfate aqueous solution of 90 grams per liters, this solution is joined one 1 liter becoming in the glue jar with L4 simultaneously in the mode that also flows, regulate the flow of aluminum sulfate aqueous solution, making into glue pH value is 8, becoming the temperature of glue process is 50 ℃, and the slurries that become glue to generate are collected in a digestion tank.Suction strainer obtains gel 143 grams, and it consists of 0.9Na
2O:Al
2O
3: 9SiO
2: 1.8SO
3: 365H
2O.Under the suction strainer condition, be that the adsorption bed ammonia nitrogen concentration is 400 milliliters of these filter cakes of drip washing of liquid after the filter after 3000 μ g/g a kind of is derived from the exchange of zeolite molecular sieve ammonium with the filter cake after filtering, the ammonia-nitrogen content in the solution after the analysis drip washing, its value is 20 μ g/g.
Table 1
Claims (7)
1, a kind of synthesis of zeolite molecular sieves may further comprise the steps: the material of a kind of synthesis zeolite of (1) preparation, one-tenth glue, crystallization are also filtered, and obtain zeolite molecular sieve; (2) step (1) is filtered the mother liquor that obtains and become glue and filtration with at least a aluminium reactant salt, obtain gel; (3) industrial wastewater that will contain ammonia nitrogen contacts the gel that obtains containing ammonia nitrogen with the gel that step (2) obtains; The all or part of material as synthesis zeolite of gel that will contain ammonia nitrogen returns step (1).
2, method according to claim 1 is characterized in that, described aluminium salt is Tai-Ace S 150, its consumption and be reacted into glue and filtering condition and make the chemical constitution of the gel that finally obtains be: rNa
2O:Al
2O
3: xSiO
2: yX:zH
2O, wherein X is SO
3, r=0.001-2, x=3-11, y=0.05-5, z=100-500.
3, method according to claim 1 is characterized in that, the described industrial wastewater that contains ammonia nitrogen is the filtered solution after the zeolite molecular sieve ammonium ion exchange, the industrial wastewater that contains ammonia nitrogen of washing discharging.
4, a kind of synthesis of zeolite molecular sieves may further comprise the steps: the material of a kind of synthesis zeolite of (1) preparation, one-tenth glue, crystallization are also filtered, and obtain zeolite molecular sieve; (2) step (1) is filtered the mother liquor that obtains and become glue and filtration with at least a aluminium reactant salt, obtain gel; (3) industrial wastewater that will contain ammonia nitrogen contacts the gel that obtains containing ammonia nitrogen with the gel that step (2) obtains; The all or part of material as synthesis zeolite of gel that will contain ammonia nitrogen returns step (1), wherein step (1) also comprises one to after the crystallization and the step carried of the slurries gas before filtering, and described gas is carried in the mother liquor that makes behind the dope filtration ammonia-nitrogen content less than 100 μ g/g.
5, method according to claim 4 is characterized in that: described gas is carried in the mother liquor that makes behind the dope filtration ammonia-nitrogen content less than 30 μ g/g.
6, a kind of synthesis of zeolite molecular sieves may further comprise the steps: the material of a kind of synthesis zeolite of (1) preparation, one-tenth glue, crystallization are also filtered, and obtain zeolite molecular sieve; (2) step (1) is filtered the mother liquor that obtains and become glue and filtration with at least a aluminium reactant salt, obtain gel; (3) industrial wastewater that will contain ammonia nitrogen contacts the gel that obtains containing ammonia nitrogen with the gel that step (2) obtains; The all or part of material as synthesis zeolite of gel that will contain ammonia nitrogen returns step (1), wherein step (1) also comprises a step to putting forward with filtration slurries gas before after the crystallization, described gas carries that ammonia-nitrogen content also comprises a step that reclaims ammonia less than 100 μ g/g in the mother liquor that makes behind the dope filtration after described gas is put forward.
7, a kind of synthesis of zeolite molecular sieves may further comprise the steps: the material of a kind of synthesis zeolite of (1) preparation, one-tenth glue, crystallization are also filtered, and obtain zeolite molecular sieve; (2) step (1) is filtered the mother liquor that obtains and become glue and filtration with at least a aluminium reactant salt, obtain gel; (3) industrial wastewater that will contain ammonia nitrogen contacts the gel that obtains containing ammonia nitrogen with the gel that step (2) obtains; The all or part of material as synthesis zeolite of gel that will contain ammonia nitrogen returns step (1), and described step (2) comprises an aged step after becoming glue and before filtering, and aging temperature is 20-95 ℃, and the time is 0.5-2 hour.
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| CN102557063B (en) * | 2012-01-16 | 2014-04-23 | 中国环境科学研究院 | Method for preparing molecular sieve by using power plant coal ash as raw materials and molecular sieve |
| CN102524160B (en) * | 2012-01-16 | 2014-08-20 | 中国环境科学研究院 | Water treatment system adopting molecular sieves prepared from flyash of power plants for filtration |
| CN111111630B (en) * | 2018-10-30 | 2022-06-03 | 中国石油化工股份有限公司 | Method for recycling waste powder in production process of adsorbent for simulated moving bed |
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| US4164551A (en) * | 1977-12-19 | 1979-08-14 | W. R. Grace & Co. | Preparation of zeolite |
| US4290895A (en) * | 1979-03-06 | 1981-09-22 | Tsuneo Iwamoto | Method for eliminating ammonia nitrogen from sewage |
| CN85108745A (en) * | 1985-05-07 | 1986-12-24 | 普鲁格列斯埃奎蒂斯有限公司 | From waste water, remove deammoniation |
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