CN1406868A - X zeolite preparation - Google Patents
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- CN1406868A CN1406868A CN 01130974 CN01130974A CN1406868A CN 1406868 A CN1406868 A CN 1406868A CN 01130974 CN01130974 CN 01130974 CN 01130974 A CN01130974 A CN 01130974A CN 1406868 A CN1406868 A CN 1406868A
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Abstract
A process for preparing X-type zeolite with low Si/Al ration and the crystal cell constant greater than or equal to 2.5 nano includes such steps as adding the mixture of sodium hydroxide and potassium hydroxide and water glass and/or aluminium source to the dregs and/or mother liquid of catalyst factor, mixing to make that the components have such mole ratios as Na2O (4-6), K2O (1-2.5), Al2O3, SiO2 (1-3) and H2O (50-250), ageing at 20-50 deg.C for 1-4 days, and hydrothermal crystallizing at 50-90 deg.C for 10-40 hr.
Description
Technical field
The present invention relates to X type prepare zeolite method, definite says so about the method that with catalyst plant waste residue and/or mother liquor is part material synthesizing low silicon aluminum ratio X type zeolite.
Background technology
X type zeolite can be used as sorbent material and detergent builder, is one of zeolite of consumption maximum.The preparation method of Gong Buing adopts water glass and sodium aluminate hydrothermal method to synthesize the earliest, is about to water glass and sodium aluminate and is mixed into behind the glue at 100 ℃ of left and right sides hydrothermal crystallizings, as described in USP2882244; The crystallization director that is adopted when also having use to synthesize NaY.The X zeolite consist of 0.9 ± 0.2M
2/nOAl
2O
32.5 ± 0.5SiO
2XH
2O (wherein M represents basic metal or alkaline earth, and n is the valence mumber of metal, and x gets and can reach any number of 8, depends on the character and the crystal hydration levels of metal M).
The lattice constant of X type zeolite is generally about 2.490nm.Reduce its silica alumina ratio and can improve performances such as loading capacity and ion-exchange.Low silica-alumina ratio X zeolite mainly is used as the active component or the high-performance water-softening chemicals of high-performance adsorbent, as described in USP5885331, USP4606899.Along with to the attention of fractionation by adsorption and the use of free phosphate detergent, this zeolite will be used widely.Document Ind.Eng.Chem.Res.2000,39, it is the most excellent by performance of the adsorbent prepared behind the low silica-alumina ratio X zeolite exchange lithium ion that 1775-1780 just thinks.But the low silica-alumina ratio X zeolite of preparation lattice constant 2.50nm is comparatively difficult technically, and cost also is higher.
Relevant lattice constant is few more than or equal to the low silica-alumina ratio X zeolite technology of preparing of 2.50 nanometers report, more representational have GB1580928 and Gunter H.Kuhl in Zeolite (1987), the 7th phase, the 451st page of title of delivering announced for the document of " Crystallization of Low-silica Fauiasite ", adopts sodium aluminate, water glass also to add the method that mixed base prepares low silica-alumina ratio X zeolite.Another kind of representational manufacture method is existing X zeolite post-processing technology, with caustic alkali the X zeolite of structure cell 2.490 nanometers prepared by USP2882244 is carried out the low silica-alumina ratio X zeolite that the hydro-thermal aftertreatment obtains structure cell 2.50 nanometers as USP5366720 announces.
For the bigger zeolite of usage quantity, adopt cheap material to synthesize and be subjected to people's attention always.Be zeolites such as feedstock production A, X and Y the most commonly with kaolin, as document D.W.Breck, Zeolite Molecular Sieves, John Wiley and Sons is described in New York one book.The prior art the most relevant with the present invention is that USP4606899 employing kaolin is silicon and aluminum source, and segmentation or dynamic crystallization obtain the low silica-alumina ratio X zeolite of lattice constant 2.50nm under the interpolation mixed base hydrothermal condition.Generally speaking be that its main quality index of raw material products obtained therefrom such as crystalline phase purity, loading capacity, loading capacity are undesirable with kaolin, easily go out stray crystal.
Catalyst plant particularly has the catalyzer manufactory of cracking catalyst kind, and all produce the mother liquor after a large amount of solid slags and the synthetic crystallization every year, mainly is SiO in the waste residue
2, Al
2O
3, RE
2O
3, Na
2O and Fe
2O
3Deng composition, and contain Cl
-, SO
4 =, F
-, Ca
++, Mg
++, P, As, Pb etc., the water content of waste residue generally surpasses 50%, its physical aspect mainly is made up of zeolite, silicon (aluminium) glue, aluminum oxide, kaolin and a small amount of clay of the cracking agent particle of various brands, various ion exchange form.Mainly contain SiO in the mother liquor after the synthetic crystallization of molecular sieve
2, Na
2O, SO
4 =, the water content of mother liquor generally reaches 90%.Because the existence of these a large amount of waste residues and mother liquor, catalyst plant has become the blowdown rich and influential family of petrochemical industry.
It is the patented technology of feedstock production NaY zeolite that the applicant once disclosed in CN1245140A by the catalyst plant waste residue.Known to the inventor, will form and constitute that all the wet waste residue of catalyst plant sial class and/or the mother liquor of more complicated are not seen as the report of preparation low silica-alumina ratio X zeolite raw material as yet without any pre-treatment.
Summary of the invention
The purpose of this invention is to provide a kind of with without the wet waste residue of any preprocessed catalyst factory sial class and/or mother liquor as the method for feedstock production lattice constant more than or equal to the low silica-alumina ratio X zeolite of 2.50 nanometers, to reduce waste residue and the waste liquid that catalyst plant was produced, improve environment, and save water glass significantly, starting material such as sodium aluminate and alkali source.
Lattice constant provided by the present invention comprises more than or equal to the low silica-alumina ratio X prepare zeolite method of 2.50 nanometers: according to the chemical constitution of waste residue and/or mother liquor, in catalyst plant waste residue and/or mother liquor, add sodium hydroxide and potassium hydroxide mixed base and water glass and/or aluminium source according to required charge ratio, and mix, make total mole of composition of gained reaction mixture meet (4.0～6.0) Na
2O: (1.0～2.5) K
2O: Al
2O
3: (1.0～3.0) SiO
2: (50～250) H
2The proportioning of O, the wherein Al in waste residue and the mother liquor
2O
3Account for the total Al of mixture
2O
30～50 heavy % of amount, the SiO in waste residue and the mother liquor
2Account for the total SiO of mixture
215～100 heavy % of amount, the alkali in waste residue and the mother liquor accounts for the 0-45% of total alkali content; With the gained mixture at 20-50 ℃ of following ageing 1-4 days, preferably 25-45 ℃ following ageing 2-3 days; With the gel after the gained ageing according to a conventional method at 50-90 ℃ of following hydrothermal crystallizing 10-40 hour, preferably 55-75 ℃ following hydrothermal crystallizing 10-25 hour.
The advantage of method provided by the present invention is not change existing zeolite production technique and equipment substantially or adopting under the situation of the existing zeolite crystallization equipment of cracking catalyst factory, reduce waste residue and mother liquor that catalyst plant produced, improve environment, and save starting material such as water glass, sodium aluminate, mixed base significantly, waste residue and mother liquor can replace 100% water glass, 0～50% aluminium sources such as sodium aluminate can be replaced, the mixed base of 0-45% can be replaced.
Description of drawings
Fig. 1 is the X-ray diffraction crystalline phase figure of embodiment 1 gained zeolite product.
Fig. 2 is the stereoscan photograph (5000 times) of embodiment 1 products obtained therefrom.
Embodiment
Low silica-alumina ratio X prepare zeolite method provided by the present invention comprises:
(1) according to the chemical constitution of waste residue and/or mother liquor, in catalyst plant waste residue and/or mother liquor, add sodium hydroxide and potassium hydroxide mixed base and water glass and/or aluminium source according to required charge ratio, and mix, make total mole of composition of gained reaction mixture meet (4.0～6.0) Na
2O: (1.0～2.5) K
2O: Al
2O
3: (1.0～3.0) SiO
2: (50～250) H
2The proportioning of O; The Al in waste residue and the mother liquor wherein
2O
3Account for the total Al of mixture
2O
30～50 heavy % of amount; SiO in waste residue and the mother liquor
2Account for the total SiO of mixture
215～100 heavy % of amount; Alkali in waste residue and the mother liquor accounts for the 0-45% of total alkali content;
(2) with (1) gained mixture at 20-50 ℃ of following ageing 1-4 days, preferably 25-45 ℃ following ageing 2-3 days;
(3) with the gel after (2) gained ageing according to a conventional method at 50-90 ℃ of following hydrothermal crystallizing 10-40 hour, preferably 55-75 ℃ following hydrothermal crystallizing 10-25 hour.
Said waste residue is the waste residue that effluxes of catalyst plant catalyst plant that the cracking catalyst kind is particularly arranged in the step in the method provided by the present invention (1), and its butt is formed SiO in (referring to the composition through gained resistates after the roasting in 800 ℃/2 hours)
2And Al
2O
3Total content should be more than or equal to 50 heavy %, preferably more than or equal to 70 heavy %, more preferably more than or equal to 80 heavy %; The water content of said waste residue has no particular limits, but preferably solid content weighs % more than or equal to 5; Its composition mainly is SiO
2, Al
2O
3, Na
2O, RE
2O
3And Fe
2O
3, and may contain Cl
-, SO
4 =, F
-, K
+, Ca
++, Mg
++, P, As, etc., the water content of waste residue generally surpasses 50 heavy %.Its physical aspect mainly by the Y zeolite of the cracking catalyst particle of various brands, various ion exchange form (as NaY, REY, HY, REHY, NH
4Y, USY, REUSY etc.), zeolite such as ZSM-5, silicon (aluminium) glue, aluminum oxide, complete synthesis or semi-synthetic carrier, and composition such as a small amount of clay.The waste residue that joins in the synthetic system not only can mainly have been decided on its composition for system provides part silicon source but also can provide part aluminium source for system.
Said mother liquor is the discharging any waste liquor after catalyst plant is particularly produced NaY or other zeolite kinds in the step in the method provided by the present invention (1), and it is formed and mainly contains SiO
2And Na
2O; Also can be the waste liquid that effluxes after molecular sieve self crystallization is filtered, it be formed and mainly contains Na
2O and K
2O.Silicon in this mother liquor and the silicon in the waste residue are jointly as the silicon source of synthesizing low silicon aluminum ratio X zeolite.The alkali in this mother liquor and the Na of interpolation
2O and K
2O is jointly as the mixing alkali source of synthesizing low silicon aluminum ratio X zeolite.
Al in the said aluminium source sodium metaaluminate preferably in the step in the method provided by the present invention (1), it and waste residue and mother liquor
2O
3Together as the Al of synthesizing low silicon aluminum ratio X zeolite
2O
3The source.
Total composition of step in the method provided by the present invention (1) gained reaction mixture meets (4.0～6.0) Na
2O: (1.0～2.5) K
2O: Al
2O
3: (1.0～3.0) SiO
2: (50～250) H
2The mole proportioning of O preferably meets (4.5～5.5) Na
2O: (1.5～2.0) K
2O: Al
2O
3: (1.5～2.5) SiO
2: (100～200) H
2The mole proportioning of O.Said Na in this specification sheets
2O and K
2O represents the basicity of mixture, and they do not comprise the part that is neutralized by acid.
The silicon source (water glass) that adds in the method provided by the present invention and the amount in aluminium source are decided according to the composition of waste residue and mother liquor fully, as long as meet the composition of needed reaction mixture, the silicon source and the aluminium source that add can add or not add less.
The said ageing of step in the method provided by the present invention (2) means placement.
In the step (3) of the inventive method, can optionally add (add or do not add) crystal seed.
The following examples will the present invention is further illustrated.
In each embodiment, the thing of the X zeolite that synthesizes adopts the X-ray diffraction method to measure mutually.The mensuration of zeolite structure cell is to measure by the RIPP145-90 standard method (to see " petrochemical complex analytical procedure (RIPP test method) ", Yang Cui waits volume surely, Science Press publishes, nineteen ninety version), chemical constitution presses RIPP134-90 and (the same) measured in the RIPP111-90 standard method, the specific surface area of zeolite and pore volume are measured by (GB/T5816-1995) method with low-temperature nitrogen adsorption method, whiteness is pressed the GB/T13176.1-91 method and is measured, crystal morphology and particle size distribution adopt scanning electron microscopic observation, and the benzene adsorptive capacity is with saturated absorption gravimetric determination afterwards.
Embodiment 1
(take between the catalyst plant integrated car of Chang Ling Na at the 880g waste residue
2O=1.83%, SiO
2=76%, Al
2O
3=32.4%, RE
2O
3=28%, SO
4 ==1.14%, Fe=0.046%, Cl
-=0.3%, solid content=15.7%) 310 milliliters of mother liquor (Na of middle adding
2The O=47 grams per liter, SiO
2=99 grams per liters), (NaOH takes from the Chang Ling catalyst plant, Na to the 710ml liquid caustic soda
2The O=298 grams per liter) and 224 gram KOH (chemically pure reagent, purity 82%, Beijing Chemical Plant), stir, treat that solid alkali dissolves the back substantially and adds 580 milliliters low basicity sodium aluminate solution (Na
2The O=147 grams per liter, Al
2O
3=90 grams per liters), stir, the stainless steel cauldron and 40 ℃ of following ageings two days later of packing in 70 ℃ of crystallization 16 hours, filters, washing, oven dry.The lattice constant of products therefrom is 2.501 nanometers, and the product chemical constitution is Na
2O=13%, K
2O=12%, SiO
2=41%, Al
2O
3=33%, RE
2O
3=0.14%, Fe
2O
3=0.15%, benzene adsorptive capacity 178mg/g, whiteness 80%.The X ray thing of the product Fig. 1 that meets each other, crystal morphology is seen Fig. 2, specific surface area 610m
2/ g, pore volume 0.378ml/g.
Comparative Examples 1
This Comparative Examples explanation is the X type prepare zeolite of raw material according to routine without waste residue or mother liquor.
144 gram liquid caustic soda (are taken from the Chang Ling catalyst plant, Na
2O=29.8%), 78 gram KOH (chemically pure reagent, purity 82%, Beijing Chemical Plant) and 175 gram deionized waters mix, and stir, and treat that solid alkali dissolves the back substantially and adds 360 grams and hang down basicity sodium metaaluminate (Na
2The O=159 grams per liter, Al
2O
3=93 grams per liters), stir, add 128 gram water glass (Na
2The O=93 grams per liter, SiO
2=293 grams per liters) pack into stainless steel cauldron and 40 ℃ of following ageings two days later in 70 ℃ of crystallization 16 hours, filter, washing, oven dry.The products therefrom lattice constant is 2.501 nanometers, and the product chemical constitution is Na
2O=13%, K
2O=12%, SiO
2=41%, Al
2O
3=33%, Fe
2O
3=0.05%, benzene adsorptive capacity 180mg/g, whiteness 95%.The product thing is similar to Fig. 1, and crystal morphology is similar to Fig. 2, specific surface area 650m
2/ g, pore volume 0.380ml/g.
The 860g waste residue (the same, Na
2O=6.7%, SiO
2=66.9%, Al
2O
3=18.6%, RE
2O
3=0.47%, Fe
2O
3=0.25%, SO
4 ==5.2%, Cl
-=0.30%, solid content 18.3%) 300 milliliters of mother liquors of middle adding (the same, Na
2The O=40 grams per liter, SiO
2=87 grams per liters), the 650ml liquid caustic soda (the same, Na
2The O=297 grams per liter), X zeolite products 10 grams of 220 gram KOH (the same), embodiment 1 gained, stir, treat solid alkali dissolve substantially the back add 730 milliliters low basicity sodium metaaluminates (the same, Na
2The O=152 grams per liter, Al
2O
3=100 grams per liters), stir, the stainless steel cauldron and 30 ℃ of following ageings after three days of packing in 60 ℃ of crystallization 24 hours, filters, washing, oven dry.The products therefrom lattice constant is 2.501 nanometers, and the product chemical constitution is Na
2O=14%, K
2O=11%, SiO
2=41%, Al
2O
3=34%, RE
2O
3=0.15%, Fe
2O
3=0.1%, benzene adsorptive capacity 170mg/g, whiteness 83%, specific surface area 590m
2/ g, pore volume 0.370ml/g.The product thing is similar to Fig. 1, and crystal morphology is similar to Fig. 2.
Embodiment 3
(take between the catalyst plant integrated car of Chang Ling Na at the 1188g waste residue
2O=7.6%, SiO
2=57.4%, Al
2O
3=23.5%, RE
2O
3=1.30%, Fe
2O
3=0.15%, SO
4 ==7.9%, Cl
-=1.50%, solid content=15.4%) middle adding 722ml liquid caustic soda (the same, Na
2The O=300 grams per liter), 210 gram KOH (the same), stir, treat solid alkali dissolve substantially the back add 590 milliliters low basicity sodium metaaluminates (the same, Na
2The O=150 grams per liter, Al
2O
3=100 grams per liters), stir, pack into stainless steel cauldron and 45 ℃ of following ageings after one day in 65 ℃ of crystallization 20 hours, filter, washing, oven dry.The products therefrom lattice constant is 2.502 nanometers, and the product chemical constitution is Na
2O=17%, K
2O=12%, SiO
2=40%, Al
2O
3=34%, RE
2O
3=0.09%, Fe
2O
3=0.07%, benzene adsorptive capacity 177mg/g, whiteness 83%, specific surface area 607m
2/ g, pore volume 0.368ml/g.The product thing is similar to Fig. 1, and crystal morphology is similar to Fig. 2.
Embodiment 4
(take between the catalyst plant integrated car of Chang Ling Na at the 1080g waste residue
2O=8.76%, SiO
2=66.15%, Al
2O
3=21.41%, RE
2O
3=1.35%, SO
4 ==5.18%, Fe=0.154%, Cl
-=1.22%, Mg=0.18%, solid content=14.7%) 100 milliliters of mother liquors of middle adding (the same, Na
2The O=35 grams per liter, SiO
2=70 grams per liters), the 677ml liquid caustic soda (the same, Na
2The O=297 grams per liter), good gels 80 grams of ageing among 220 gram KOH (the same) and the embodiment 1, stir, treat that solid alkali dissolves the back substantially and adds 680 milliliters low basicity sodium metaaluminate (Na
2The O=150 grams per liter, Al
2O
3=100 grams per liters), stir, pack into stainless steel cauldron and 30 ℃ of following ageings after three days in 60 ℃ of crystallization 24 hours, filter, washing, oven dry.The products therefrom lattice constant is 2.503 nanometers, and the product chemical constitution is Na
2O=17%, K
2O=11%, SiO
2=42%, Al
2O
3=33%, RE
2O
3=0.15%, Fe
2O
3=0.1%, benzene adsorptive capacity 171mg/g, whiteness 81%, specific surface area 590m
2/ g, pore volume 0.369ml/g.The product thing is similar to Fig. 1, and crystal morphology is similar to Fig. 2.
1167 milliliters of mother liquors (the same, Na
2The O=45 grams per liter, SiO
2Adding 335ml liquid caustic soda=90 grams per liters) (the same, Na
2The O=297 grams per liter) and 220 gram KOH (the same), stir, treat that solid alkali dissolves the back substantially and adds 1020 milliliters low basicity sodium metaaluminate (Na
2The O=150 grams per liter, Al
2O
3=100 grams per liters), stir, pack into stainless steel cauldron and 35 ℃ of following ageings after three days in 65 ℃ of crystallization 20 hours, filter, washing, oven dry.The products therefrom lattice constant is 2.50 nanometers, and the product chemical constitution is Na
2O=15%, K
2O=13%, SiO
2=41%, Al
2O
3=33%, RE
2O
3=0.18%, Fe
2O
3=0.11%, benzene adsorptive capacity 169mg/g, whiteness 89%, specific surface area 593m
2/ g, pore volume 0.357ml/g.The product thing is similar to Fig. 1, and crystal morphology is similar to Fig. 2.
(take between the catalyst plant integrated car of Chang Ling Na at the 1030g waste residue
2O=10.5%, SiO
2=54.8%, Al
2O
3=16.1%, RE
2O
3=1.28%, SO
4 ==7.85%, Cl
-=1.50%, solid content=18.6%) middle adding 300ml liquid caustic soda (the same, Na
2The O=297 grams per liter), 116 gram KOH (the same) and 1000 milliliters of mother liquor (K that embodiment 1-5 discharges
2The O=57 grams per liter, Na
2The O=124 grams per liter), stirs, treat that solid alkali dissolves the back substantially and adds 610 milliliters low basicity sodium metaaluminate (Na
2The O=150 grams per liter, Al
2O
3=100 grams per liters), stir, pack into stainless steel cauldron and 35 ℃ of following ageings after three days in 65 ℃ of crystallization 20 hours, filter, washing, oven dry.The products therefrom lattice constant is 2.50 nanometers, and the product chemical constitution is Na
2O=17%, K
2O=11%, SiO
2=43%, Al
2O
3=33%, RE
2O
3=0.28%, Fe
2O
3=0.13%, benzene adsorptive capacity 165mg/g, whiteness 81%, specific surface area 617m
2/ g, pore volume 0.359ml/g.The product thing is similar to Fig. 1, and crystal morphology is similar to Fig. 2.
Claims (8)
1, a kind of lattice constant is characterized in that more than or equal to the low silica-alumina ratio X prepare zeolite method of 2.50 nanometers this method comprises:
(1) according to the chemical constitution of waste residue and/or mother liquor, in catalyst plant waste residue and/or mother liquor, add sodium hydroxide and potassium hydroxide mixed base and water glass and/or aluminium source according to required charge ratio, and mix, make total mole of composition of gained reaction mixture meet (4.0～6.0) Na
2O: (1.0～2.5) K
2O: Al
2O
3: (1.0～3.0) SiO
2: (50～250) H
2The proportioning of O; The Al in waste residue and the mother liquor wherein
2O
3Account for the total Al of mixture
2O
30～50 heavy % of amount; SiO in waste residue and the mother liquor
2Account for the total SiO of mixture
215～100 heavy % of amount; Alkali in waste residue and the mother liquor accounts for the 0-45% of total alkali content;
(2) with (1) gained mixture at 20-50 ℃ of following ageing 1-4 days;
(3) with the gel after (2) gained ageing at 50-90 ℃ of following hydrothermal crystallizing 10-40 hour.
2, according to the process of claim 1 wherein said waste residue in the step (1) be have the catalyst of cracking petroleum kind catalyst plant efflux waste residue, SiO during its butt is formed
2And Al
2O
3Total content more than or equal to 50 heavy %.
3, according to the method for claim 2, SiO during wherein the butt of said waste residue is formed
2And Al
2O
3Total content more than or equal to 70 heavy %.
4, according to the method for claim 3, SiO during wherein the butt of said waste residue is formed
2And Al
2O
3Total content more than or equal to 80 heavy %.
5, according to the process of claim 1 wherein the physical aspect of said waste residue comprise the catalyst of cracking petroleum particle, with Na
+, H
+, NH
4 +With rare earth ion be molecular sieve, silica gel or the alumino silica gel, aluminum oxide and the clay that contain y-type zeolite and/or ZSM-5 zeolite of ionic forms.
6, according to the process of claim 1 wherein that said mother liquor in the step (1) is the discharging any waste liquor after catalyst plant is produced NaY or other zeolites, it mainly consists of SiO
2And Na
2O.
7, according to the process of claim 1 wherein that said aluminium source is a sodium metaaluminate in the step (1).
8, according to the process of claim 1 wherein that the mole of the middle gained reaction mixture of step (1) consists of (4.5～5.5) Na
2O: (1.5～2.0) K
2O: Al
2O
3: (1.5～2.5) SiO
2: (100～200) H
2O.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011309741A CN1171789C (en) | 2001-08-29 | 2001-08-29 | X zeolite preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB011309741A CN1171789C (en) | 2001-08-29 | 2001-08-29 | X zeolite preparation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1406868A true CN1406868A (en) | 2003-04-02 |
| CN1171789C CN1171789C (en) | 2004-10-20 |
Family
ID=4670284
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB011309741A Expired - Fee Related CN1171789C (en) | 2001-08-29 | 2001-08-29 | X zeolite preparation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1171789C (en) |
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| CN1323944C (en) * | 2005-08-02 | 2007-07-04 | 洛阳市建龙化工有限公司 | Process method of improved 13X molecular screen |
| CN102107881B (en) * | 2009-12-23 | 2012-12-12 | 深圳市海川实业股份有限公司 | Method for preparing NaX zeolite |
| CN102896000A (en) * | 2011-07-29 | 2013-01-30 | 中国石油化工股份有限公司 | Method for utilizing residues of catalyst production |
| CN105536696A (en) * | 2015-12-15 | 2016-05-04 | 湖南理工学院 | Adsorbent for removing heavy metals and ammonia nitrogen in waste water as well as preparation method thereof |
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| CN110627088A (en) * | 2018-06-21 | 2019-12-31 | 中国科学院大连化学物理研究所 | Recycling method of low-silicon X molecular sieve synthesis mother liquor |
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| CN114105165A (en) * | 2021-12-21 | 2022-03-01 | 中科催化新技术(大连)股份有限公司 | Method for recycling synthetic mother liquor of low-silica-alumina-ratio X-type molecular sieve |
-
2001
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| CN1323944C (en) * | 2005-08-02 | 2007-07-04 | 洛阳市建龙化工有限公司 | Process method of improved 13X molecular screen |
| CN102107881B (en) * | 2009-12-23 | 2012-12-12 | 深圳市海川实业股份有限公司 | Method for preparing NaX zeolite |
| CN102896000A (en) * | 2011-07-29 | 2013-01-30 | 中国石油化工股份有限公司 | Method for utilizing residues of catalyst production |
| CN102896000B (en) * | 2011-07-29 | 2014-08-20 | 中国石油化工股份有限公司 | Method for utilizing residues of catalyst production |
| CN105536696A (en) * | 2015-12-15 | 2016-05-04 | 湖南理工学院 | Adsorbent for removing heavy metals and ammonia nitrogen in waste water as well as preparation method thereof |
| CN105536696B (en) * | 2015-12-15 | 2019-01-25 | 湖南理工学院 | A kind of preparation method for the adsorbent removing heavy metal in waste water and ammonia nitrogen |
| CN105731487A (en) * | 2016-03-07 | 2016-07-06 | 四川理工学院 | Method for resource utilization of exhaust gas alkaline-washing waste residues generated in polysilicon production |
| CN105731487B (en) * | 2016-03-07 | 2018-02-09 | 四川理工学院 | A kind of method utilized to waste gas in production of polycrystalline silicon alkali cleaning waste residue resource |
| CN110627088A (en) * | 2018-06-21 | 2019-12-31 | 中国科学院大连化学物理研究所 | Recycling method of low-silicon X molecular sieve synthesis mother liquor |
| CN110963501A (en) * | 2019-12-26 | 2020-04-07 | 河北欣芮再生资源利用有限公司 | X-type molecular sieve with high added value, preparation method and application thereof |
| CN110963501B (en) * | 2019-12-26 | 2021-09-24 | 河北欣芮再生资源利用有限公司 | X-type molecular sieve with high added value, preparation method and application thereof |
| CN114105165A (en) * | 2021-12-21 | 2022-03-01 | 中科催化新技术(大连)股份有限公司 | Method for recycling synthetic mother liquor of low-silica-alumina-ratio X-type molecular sieve |
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