CN1107646C - Preparation of A-type zeolite - Google Patents
Preparation of A-type zeolite Download PDFInfo
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- CN1107646C CN1107646C CN99125943A CN99125943A CN1107646C CN 1107646 C CN1107646 C CN 1107646C CN 99125943 A CN99125943 A CN 99125943A CN 99125943 A CN99125943 A CN 99125943A CN 1107646 C CN1107646 C CN 1107646C
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Abstract
The present invention relates to a preparation method for A-shaped zeolite, which is characterized in that the method comprises the following steps: water is added to waste slag containing silicon and/or aluminum in a catalyst plant for beating, and other silicon sources are added or not added to the waste slag; afterwards, aluminate is added towards the waste slag and is uniformly mixed, and then, acidic aluminum salt, acid or alkali is used for adjusting the alkalinity of batch feeding in order to make the molar composition of reaction mixture finally obtained accord with the proportioning of (2.0 to 4.0) Na2O: Al2O3: (1.8 to 3.5) SiO2: (80 to 200) H2O, wherein Al2O3 in the waste slag takes 0 to 45% of the total amount of Al2O3 of the mixed material, and the SiO2 in the waste slag takes 55 to 100% of the total amount of SiO2 of the mixing material; then, water-heat crystallization is carried out to the obtained reaction mixture by a conventional method. When the method is used, the waste slag generated by the catalyst plant can be digested, environments are improved, and the cost is reduced.
Description
The present invention relates to A type prepare zeolite method, what also relate to silicon-aluminum containing class waste residue utilizes method again.
A type zeolite can be used as sorbent material and detergent builder, is the zeolite of consumption maximum.General water glass and the sodium aluminate hydrothermal method of adopting synthesized (as USP2,882,243, described in the CN86106033A), is about to water glass and sodium aluminate and is mixed into behind the glue at 100 ℃ of left and right sides hydrothermal crystallizings, and wherein CN86106033A has also adopted two sections temperature crystallization.In order to pursue less crystalline size, the crystallization director that is adopted when also having use to synthesize NaY.1986 the 4th phase page 1 of the 22nd page of " daily chemical industry " 1987 the 3rd phase and " daily chemical industry " have all been reported crystallization director used when using similar NaY zeolite synthesis, crystal grain can be narrowed down to average 1.5 microns by average 4 microns, shorten crystallization time again.Because A type zeolite usage quantity is bigger, the research of adopting more cheap material to synthesize the A zeolite is subjected to people's attention always, preparing the A zeolite with kaolin is a research that comes into one's own, that reports is also more, as CN1064850A, USP4,075,280, Japanese kokai publication sho 53-16398 etc., it is characterized in that with kaolin be main silicon and aluminum source, add crystallization acquisition A type zeolite under the alkaline matter hydrothermal condition, generally speaking its main quality index such as crystalline phase purity, loading capacity, loading capacity and whiteness etc. will be lower than the product of water glass, sodium aluminate hydrothermal method.
Catalyst plant particularly has the catalyzer manufactory of cracking catalyst kind, all produces a large amount of solid slags every year, wherein mainly is SiO
2, Al
2O
3, RE
2O
3, Na
2O and Fe
2O
3Etc. component, and may contain Cl
-, SO
4 =, Ca
++, Mg
++, F
-, impurity such as P, As, Pb, wherein SiO
2And Al
2O
3Sum accounts for more than the 50 heavy % of waste residue solids, the water content of waste residue generally also surpasses 50 heavy %, its physical aspect mainly by the molecular sieve of the granules of catalyst of various brands, various ion exchange form, silicon (aluminium) glue, aluminum oxide, complete synthesis or semi-synthetic carrier, and a small amount of clay etc. form, become the blowdown rich and influential family of petrochemical industry.The technology that relates to controlling waste residue in the prior art and utilize is more, physical methods such as the shaping of employing, briquetting are arranged, as CN1051523A with waste residue as material of construction and filler, but very high to water content, as may to contain heavy metal element catalyst plant waste residue is just not too suitable; From waste residue, extract the technology of useful component for another example, from the waste residue that contains rare earth, extract rare earth such as CN1044635A, but can not be all effective to various components, can not complete digestion fall waste residue, even increase the amount of waste residue owing to treating processes.
It is more that the waste residue that relates to silicon, aluminium and be main component is used for preparing the technology of zeolite.Particularly relate to the A zeolites or associated technology mainly contains: JP5155611 will contain SiO
2And Al
2O
3Inorganic or organic waste fusion and be added to the alkali of equivalent at least such as sodium hydroxide in boil and be used to prepare zeolite, waste residue is SiO preferably
2/ Al
2O
3=2～4 sludge or its incineration ash; JP5221628, JP6256012, JP6239612 are also similar substantially; This method is not suitable for the catalyst plant waste residue, because very big catalyst plant waste residue elder generation fusion obviously is uneconomic for water content.EP451112A will be less than 300 microns sial waste material with about 20% H
2SO
4Solvent and solute weight ratio 1.3～6 and 150～230 ℃ of following processing 0.25～0.75 hour, be cooled to 60～150 ℃ then, use alkali such as sodium-hydroxide treatment again, and in every liter, add 0.2～0.5 the gram flocculation agent, time obtain silicon-aluminium glue body in PH3.5～4.5, a ℃ following reaction obtains zeolite in pH=8～13 and 60～200 for hydro-oxidation sodium and water, and zeolite type depends on the mixture composition.J5514412 adds flocculation agent and adjusts the basicity crystallization with silicate and sodium-hydroxide treatment aluminum oxide sludge to go out zeolite again, and characteristics are earlier with acid or alkaline purification and add flocculation agent.What difference was little with it is that USP4310496 dissolves the silicon-dioxide formation alkalimetal silicate that contains useless cigarette ash with alkali hydroxide soln down at 60～110 ℃, isolate to be regardless of with gac or oxygenant and separate component, at room temperature with the alkali metal aluminate reaction and stir 8～48 hours crystallization down at 70～100 ℃ and obtain Y zeolite.USP4784980 adopts sodium hydroxide and sodium aluminate and solid spent catalyst to carry out long-time two-stage reaction to remove part metals vanadium and nickel and to form zeolite A or P with useless Preparation of Catalyst A type zeolite.USP4055622 prepares A type zeolite with aluminium making residue, and its waste residue is actual only as the aluminium source.Known to the inventor, the wet waste residue of the catalyst plant sial class of forming more complicated is not seen as the report of preparation NaA zeolite raw material as yet without any pre-treatment, the improvement technology that the complete digestion of catalyst plant waste residue is fallen is not reported yet.
The purpose of this invention is to provide a kind of is that the method that catalyst plant effluxes waste residue is fallen in feedstock production NaA zeolite and complete digestion with the wet waste residue of catalyst plant siliceous, the aluminium class, to reduce pollution to environment, simultaneously guaranteeing to save starting material under the prerequisite that product quality does not descend significantly, lowering the manufacturing cost of A zeolite.
A type prepare zeolite method provided by the present invention comprises: with siliceous and/or aluminium the catalyst plant waste residue add water making beating, add or do not add other silicon source (as water glass), to wherein adding aluminate and mixing, use acid aluminium salt, acid (as mineral acid) or alkali (as sodium hydroxide) to adjust the basicity that feeds intake again and make the mole composition of last gained reaction mixture meet (2.0～4.0) Na then
2O: Al
2O
3: (1.8～3.5) SiO
2: (80～200) H
2O, preferred (2.3～3.2) Na
2O: Al
2O
3: (1.9～2.1) SiO
2: (100～185) H
2The proportioning of O, the wherein Al in the waste residue
2O
3Account for the total Al of mixture
2O
30～45 heavy % of amount, the SiO in the waste residue
2Account for the total SiO of mixture
255～100 heavy % of amount; Then with gained reaction mixture hydrothermal crystallizing according to a conventional method.
Said reaction mixture can contain mole non-imposedly and consists of (15～17) Na in the A type prepare zeolite method provided by the present invention
2O: Al
2O
3: (14～16) SiO
2: (200～350) H
2The faujusite directed agents (crystal seed) of O, each contained component counts in total composition of last said reaction mixture in this directed agents, the Al in the directed agents
2O
3Account for the total Al of mixture
2O
30～7 heavy % of amount; This faujusite directed agents can prepare by the whole bag of tricks of preparation faujusite directed agents in the prior art, but preferably the method for preparing directed agents that is adopted among the conventional preparation method according to the NaY zeolite of industrial common employing at present prepares, and for example prepares according to the method for preparing directed agents that is proposed among USP3639099, USP3671191, USP4166099 and the CN1081425A.
In the Catalysts and its preparation method provided by the present invention said siliceous and/or aluminium waste residue be the waste residue that effluxes of catalyst plant catalyst plant that the catalyst of cracking petroleum kind is particularly arranged, its butt is formed SiO in (referring to the composition through gained resistates after 800 ℃ of roastings in 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 %; Said waste residue can contain rare earth, also can contain iron, calcium, magnesium and Cl
-, SO
4 =, F
-Deng impurity; The water content of said waste residue has no particular limits, but preferably solid content weighs % more than or equal to 5; This waste residue mainly by the cracking catalyst particle of various brands, various ion exchange form (as Na
+, H
+, NH
4 +And rare earth ion) comprise that Y zeolite is (as NaY, REY, HY, REHY, NH
4Y, USY, REUSY etc.) and the ZSM-5 zeolite form in clay-type substance such as interior molecular sieve, silica gel or alumino silica gel, aluminum oxide and kaolin, metakaolins.This waste residue can also can directly add the water making beating without grinding through processing such as grindings when being used to prepare catalyzer.
The said aluminate suitable sodium aluminate of basicity preferably in the A type prepare zeolite method provided by the present invention; The basicity that adjustment feeds intake can be used Tai-Ace S 150, aluminum phosphate, aluminum chloride, aluminum nitrate, phosphoric acid, sulfuric acid, hydrochloric acid, nitric acid or sodium hydroxide, preferably only uses the suitable sodium aluminate of basicity, can simplify feeding intake like this; Al in they and waste residue and the directed agents
2O
3Together as the aluminium source of synthesizing the NaA zeolite.The adding of all raw materials all must meet last total composition of said reaction mixture; Na during this is formed
2O represents the basicity of mixture, does not comprise the part that is neutralized by acid.
Said hydrothermal crystallizing carries out according to the condition of prior art in the method provided by the invention, generally is at 80-120 ℃ of following hydrothermal crystallizing 2-20 hour.
The advantage of method provided by the present invention is not change existing conventional NaA zeolite production technique and equipment substantially or adopting under the situation of the existing Y zeolite crystallization apparatus of cracking catalyst factory, the waste residue that catalyst plant produced is fallen in digestion, improve environment, and save starting material such as water glass, sodium aluminate significantly, waste residue can replace 55～100% water glass, can replace aluminium sources such as 0～45% sodium aluminate, Tai-Ace S 150.It is the quality of the NaA zeolite of raw material gained that gained NaA zeolite quality is not less than with kaolin.
The NaA type zeolite of the inventive method gained can be applied to the applicable all areas of conventional A type molecular sieve, as sorbent material, and siccative, water-softening chemicals etc.
Fig. 1 is X-ray diffraction (XRD) the crystalline phase figure of the embodiment of the invention 1 products obtained therefrom.
The following examples will the present invention is further illustrated.
In each embodiment, the thing phase and the relative crystallinity of the NaA zeolite that synthesizes are analyzed with X-ray diffraction (XRD) method, and with diffraction peak height between the 2 θ angle of diffraction 20～30 and Comparative Examples 1 relatively draw relative crystallinity, sample through the thermal treatment of the same terms as 110 ℃ 2 hours dry to eliminate the influences of planar water; Chemical constitution is measured (seeing " petrochemical complex analytical procedure (RIPP test method) ", volumes such as Yang Cuiding, Science Press, nineteen ninety) by RIPP 134-90 standard method; The ultimate analysis of calcium is pressed RIPP116-90 (the same) standard method and is measured; The calcium exchange capacity condition determination is: according to zeolite: calcium chloride: the condition of water=1: 1: 20 with gained A type zeolite 90 ℃ of exchanges 1 hour, then by measuring the amount that calcium content on the zeolite of exchange back draws every gram zeolite exchange calcium; The whiteness of zeolite is pressed the GB/T13176.1-91 standard method and is measured, and the methyl alcohol adsorptive capacity is with saturated absorption gravimetric determination afterwards.
Embodiment 1
With 360ml water glass (SiO
2=250g/L, modulus 3.2, Chang Ling catalyst plant product) and the high basicity sodium metaaluminate of 243.5ml (Al
2O
3=40g/L, Na
2O=287g/L, Chang Ling catalyst plant product) mix, its mole consists of 16Na
2O: Al
2O
3: 15SiO
2: 320H
2O adds the 100.6ml deionized water with its ageing at room temperature after 18 hours, the back that stirs is as directed agents.
At the low basicity sodium metaaluminate (Al of 233.5ml
2O
3=100g/L, Na
2O=150g/L, Chang Ling catalyst plant product, down with) in add 292g catalyst plant waste residue and (take between the catalyst plant integrated car of Chang Ling Na
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 13.6%, and 24.2gNaOH (Beijing Chemical Plant's reagent, chemical pure proportion 1.015) and the above-mentioned directed agents of 120ml,, together following) and the 50ml deionized water, pack into after stirring in the stainless steel sealed reactor, and 100 ℃ of following crystallization 5 hours, filter, after the washing, oven dry, the XRD thing of the products therefrom Fig. 1 that meets each other, its chemical constitution is Na
2O=16.5%, SiO
2=32.8%, Al
2O
3=27.9%, H
2O=22%, RE
2O
3=0.28%, Fe
2O
3=0.43%, comparing its relative crystallinity with Comparative Examples 1 product is 95%, and its methyl alcohol adsorptive capacity is 170mg/g, and whiteness is 85, and calcium exchange capacity is that 295mg/g is (with CaCO
3Meter).
Comparative Examples 1
Press the method preparation of 1986 the 4th phase page 1 of document " daily chemical industry ", water glass among 44 milliliters of embodiment 1 and 94 ml waters are warming up to 40 ℃, low basicity sodium metaaluminate among 102 milliliters of embodiment 1 and 100 ml waters also are warming up to 40 ℃, and above-mentioned two liquid are mixed, add 10 milliliters of crystallization directors among the embodiment 1 again, 100 ℃ of following crystallization 2 hours, the product relative crystallinity is as 100%, record its whiteness＞95, methyl alcohol adsorptive capacity 180mg/g, calcium exchange capacity 325mg/g is (with CaCO
3Meter).
Comparative Examples 2
Press the method preparation of the embodiment 1 among the document CN1064850A, 16 milliliter 25% aqueous sodium hydroxide solution and 50 gram kaolin (Suzhou carclazyte) are mixed, and fed 150 ℃ of steam crystallization 6 hours, products therefrom relative crystallinity＜80%, recording its whiteness is 90, the methyl alcohol adsorptive capacity is 150mg/g, and calcium exchange capacity is that 285mg/g is (with CaCO
3Meter).
In the low basicity sodium metaaluminate (with embodiment 1) of 454ml, add the 805g waste residue and (take between the catalyst plant integrated car of Chang Ling Na
2O=5.4%, SiO
2=78.0%, Al
2O
3=17.4%, RE
2O
3=0.47%, Fe
2O
3=0.1%, SO
4 ==6.5%, Cl
-=0.99%, solid content 14.9%), 94gNaOH and 150ml deionized water, after stirring, the stainless steel sealed reactor and 100 ℃ of following crystallization 6 hours of packing into filters, after the washing, oven dry, the chemical constitution of products therefrom is Na
2O=17.5%, SiO
2=33.8%, Al
2O
3=28.1%, H
2O=19%, RE
2O
3=0.11%, Fe
2O
3=0.04%, comparing its relative crystallinity with Comparative Examples 1 product is 91%, records its methyl alcohol adsorptive capacity 168mg/g, whiteness 80%, and calcium exchange capacity 290mg/g is (with CaCO
3Meter).
Embodiment 3
In the low basicity sodium metaaluminate (with embodiment 1) of 334ml, add the 800g waste residue and (take between the catalyst plant integrated car of Chang Ling Na
2O=6.8%, SiO
2=68.6%, Al
2O
3=18.4%, Cl
-=1.05%, solid content 13.7%), 55gNaOH and 150ml deionized water, after stirring, the stainless steel sealed reactor and 100 ℃ of following crystallization 6 hours of packing into filters, after the washing, oven dry, the products therefrom chemical constitution is Na
2O=18.1%, SiO
2=33.4%, Al
2O
3=28.3%, H
2O=19%, RE
2O
3=0.21%, Fe
2O
3=0.55%, with Comparative Examples 1 product its to compare relative crystallinity be 93%, methyl alcohol adsorptive capacity 170mg/g, whiteness 80%, calcium exchange capacity 295mg/g is (with CaCO
3Meter).
Embodiment 4
At 400ml Tai-Ace S 150 (Chang Ling catalyst plant product, Al
2O
3Content 90g/L, proportion 1.27g/ml) adds the 800g waste residue in and (take between the catalyst plant integrated car of Chang Ling Na
2O=7.6%, SiO
2=77.4%, Al
2O
3=13.5%, RE
2O
3=1.30%, Fe
2O
3=0.15%, SO
4 ==7.9%, Cl
-=1.50%, solid content 15.4%), 237gNaOH and 500ml deionized water, after stirring, the stainless steel sealed reactor and 100 ℃ of following crystallization 6 hours of packing into filters, after the washing, oven dry, the products therefrom chemical constitution is Na
2O=16.9%, SiO
2=34.4%, Al
2O
3=27.9%, H
2O=20%, RE
2O
3=0.11%, Fe
2O
3=0.05%, comparing its relative crystallinity with Comparative Examples 1 product is 90%, methyl alcohol adsorptive capacity 171mg/g, and whiteness 85%, calcium exchange capacity 290mg/g is (with CaCO
3Meter).
Embodiment 5
In 200ml Tai-Ace S 150 (with embodiment 4) and the low sodium metaaluminate (with embodiment 1) of 200ml, add the 800g waste residue and (take between the catalyst plant integrated car of Chang Ling Na
2O=6.7%, SiO
2=66.9%, Al
2O
3=11.6%, RE
2O
3=0.47%, Fe
2O
3=0.25%, SO
4 ==5.2%, Cl
-=0.30%, solid content 18.3%), 154gNaOH and 300ml deionized water, after stirring, the stainless steel sealed reactor and 100 ℃ of following crystallization 5 hours of packing into filters, after the washing, oven dry, the product chemical constitution is Na
2O=17.1%, SiO
2=33.4%, Al
2O
3=26.9%, H
2O=22%, RE
2O
3=0.05%, Fe
2O
3=0.15%, comparing its relative crystallinity with Comparative Examples 1 product is 94%, methyl alcohol adsorptive capacity 174mg/g, and whiteness 80%, calcium exchange capacity 298mg/g is (with CaCO
3Meter).
Embodiment 6
In 842ml sodium aluminate (with embodiment 4), add the 800g waste residue and (take between the catalyst plant integrated car of Chang Ling Na
2O=12.8%, SiO
2=84.2%, Al
2O
3=0, RE
2O
3=0.14%, Fe
2O
3=0.12%, SO
4 ==5.6%, Cl
-=0.37%, solid content 14.7%), after stirring, the stainless steel sealed reactor and 100 ℃ of following crystallization 6 hours of packing into filters, after the washing, oven dry, and the products therefrom chemical constitution is Na
2O=16.7%, SiO
2=34.6%, Al
2O
3=27.1%, H
2O=21%, RE
2O
3=0.1%, Fe
2O
3=0.07%, comparing its relative crystallinity with Comparative Examples 1 product is 95%, methyl alcohol adsorptive capacity 175mg/g, and whiteness 85%, calcium exchange capacity 295mg/g is (with CaCO
3Meter).
Claims (10)
1, a kind of A type prepare zeolite method, it is characterized in that this method comprises: the catalyst plant waste residue of siliceous and/or aluminium is added the water making beating, add or do not add other silicon source, to wherein adding aluminate and mixing, the basicity that feeds intake with acid aluminium salt, acid or alkali adjustment makes the mole composition of last gained reaction mixture meet (2.0～4.0) Na more then
2O: Al
2O
3: (1.8～3.5) SiO
2: (80～200) H
2The proportioning of O, the wherein Al in the waste residue
2O
3Account for the total Al of mixture
2O
30～45 weight % of amount, the SiO in the waste residue
2Account for the total SiO of mixture
255～100 weight % of amount; Then with gained reaction mixture hydrothermal crystallizing according to a conventional method.
2, according to the process of claim 1 wherein that said reaction mixture contains mole and consists of (15～17) Na
2O: Al
2O
3: (14～16) SiO
2: (200～350) H
2The faujusite directed agents of O, each contained component counts in total composition of last said reaction mixture in this directed agents, the Al in the directed agents
2O
3Account for the total Al of mixture
2O
30～7 weight % of amount.
3, according to the process of claim 1 wherein said catalyst plant waste residue siliceous and/or aluminium 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 weight %, this waste residue through milled processed, or directly adds the water making beating without grinding when being used to prepare catalyzer.
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 70 weight %.
5, 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 weight %.
6, 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 +Or rare earth ion is molecular sieve, silica gel or the alumino silica gel, the aluminum oxide that comprise y-type zeolite and ZSM-5 zeolite of ionic forms and the clay that comprises kaolin, metakaolin.
7, according to the process of claim 1 wherein that said other silicon source is a water glass.
8, according to the process of claim 1 wherein that said aluminate is a sodium metaaluminate.
9, according to the process of claim 1 wherein that said acid aluminium salt is Tai-Ace S 150, aluminum phosphate, aluminum chloride or aluminum nitrate.
10, according to the process of claim 1 wherein that the mole composition of last gained reaction mixture meets (2.3～3.2) Na
2O: Al
2O
3: (1.9～2.1) SiO
2: (100～185) H
2The proportioning of O.
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| CN111498863B (en) * | 2020-03-19 | 2021-12-31 | 复榆(张家港)新材料科技有限公司 | Process for preparing high-crystallinity H-ZSM-5 zeolite by using waste catalyst |
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| CN1299778A (en) | 2001-06-20 |
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