CN102091648A - Method for preparing carclazyte olefin removing catalyst - Google Patents
Method for preparing carclazyte olefin removing catalyst Download PDFInfo
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Abstract
The invention provides a method for preparing a carclazyte olefin removing catalyst. The method is characterized by comprising the following steps: treating the porous clays as raw materials with sulfuric acid to obtain carclazyte with crystal transition activity; mixing the carclazyte with crystal transition activity with solid caustic soda; adding a dispersing agent, an extrusion assistant and a peptizing agent to the mixture; kneading and mixing the mixture uniformly; carrying out extrusion molding on the mixture on an extruder or rolling the mixture on a rolling machine; drying and roasting molded bodies, then carrying out hydrothermal crystallization reaction in the presence of sodium silicate, sodium hydroxide, deionized water, a guiding agent and the like to obtain the crystallization product with higher NaY zeolite content and silica and alumina and smaller grain size; and carrying out ion exchange and hydrothermal ultrastable modification on the crystallization product to obtain the carclazyte olefin removing catalyst with low production cost and high catalytic activity and selectivity.
Description
Technical field
The present invention relates to catalysis technical field, relate to a kind of preparation method of olefinic hydrocarbon expelling catalyzer, be a kind of preparation method of full white-clay type olefinic hydrocarbon expelling catalyzer, saying so a kind of more specifically is the method for the full white-clay type olefinic hydrocarbon expelling catalyzer of feedstock production with the Concave-convex clay rod.
Background technology
In early days, industrially remove that trace amounts of olefin mainly adopts hydrofining technology in the reformed oil, promptly utilize noble metal platinum or palladium to load on and make catalyst on the aluminium oxide, behind catalytic reforming reaction, carry out " back end hydrogenation " thus process is to realize making the saturated purpose that removes alkene that reaches of alkene, typical catalyst has CN85100760A, CN85100215A, CN1448474A, CN101260320A patent report.Experimental result shows: adopt " back end hydrogenation " no matter technology is all relatively good for its active component effect with platinum or palladium for single benzene cut, but for the wide component product of the aromatic hydrocarbons that contains benzene,toluene,xylene simultaneously, the hydrogenation reaction degree of depth is difficult to take into account comprehensively, can cause the loss of aromatic hydrocarbon product serious, and carried noble metal rear catalyst cost is higher; " back end hydrogenation " arts demand is operated under hydro condition and is consumed hydrogen, the process route complexity, and equipment investment expense height influences its further commercial Application.
At present, industrial extensive employing granular carclazyte process for refining removes alkene, and these carclazytes mainly are back formation of sieve and silica-sesquioxide mixing by unbodied or crystallization.This technology be utilize carclazyte abundant microporous duct, than large pore volume and the surface acidity, its surface acidity can make alkene generation polymerization and the alkylated reaction in the aromatic hydrocarbons generate the bigger species of molecular weight, wherein a part is adsorbed by the duct that granular carclazyte enriches, and some is removed in follow-up separation process.But the in use easy inactivation of carclazyte, operation cycle is short, carclazyte behind the inactivation can not be regenerated, the general carclazyte that just need more renew in 2～3 months, the frequent carclazyte of changing not only causes the aromatic hydrocarbons loss and increases workload, and a large amount of useless carclazytes can only be handled serious environment pollution by the mode of landfill.
Molecular sieve is manually synthetic zeolite, the crystal of alumino-silicate, and with its unique pore canal system, superior acidity, good adsorption performance become very important catalyst in the industry.The aperture of molecular sieve is bigger, can hold bigger aromatic hydrocarbon molecule of molecular diameter and alkene at its duct internal reaction; The superior acidity of molecular sieve promotes long-chain olefin and aromatic hydrocarbons to carry out alkylated reaction; The heat endurance of molecular sieve and hydrothermally stable are good, so structure remains unchanged during high temperature regeneration, and regenerability is better.Because molecular sieve possesses above advantage, make catalyst and possess the catalytic activity height, long service life, thus improve the deolefination effect, reduce catalyst and change number of times, catalyst integral production cost is low, and environmental pollution is little.
EP0895977A1 has announced with the molecular sieve to be that active component and aluminium oxide are the preparing carriers olefinic hydrocarbon expelling catalyzer.Wherein the molecular sieve active component is selected from Y zeolite, Beta molecular sieve, SSZ-25 molecular sieve, SSZ-26 molecular sieve, SSZ-33 molecular sieve.
US6617482 disclose with MCM series and the serial molecular sieve of faujasite be active component remove the trace amounts of olefin catalyst.
W001/30942A1 discloses in a kind of utilization pore size molecular sieve MCM-22 and has prepared olefinic hydrocarbon expelling catalyzer for active component and clay carrier moulding.
US4795550 reported with the Y zeolite be active component remove the trace amounts of olefin catalyst, wherein molecular sieve content is 10～90% in the catalyst.
CN1618932A has described under conditions of non-hydrogen, and the employing molecular sieve is an active component, and aluminium oxide or kaolin are the preparing carriers olefinic hydrocarbon expelling catalyzer.The molecular sieve active component is selected from Beta molecular sieve, Y zeolite, SAPO molecular sieve, ZSM-5 molecular sieve, SRCY molecular sieve or super stable molecular sieve.
CN101433856A discloses the compound olefine lowering catalyst that adds one or more elements of lanthanide rare, P, W, Nb, Mo in modification Y or beta-molecular sieve and alumina mixture.
It is that the synthetic Y zeolite of crystallization takes place for raw material and sodium metasilicate etc. that UK1271450 has described with kaolin.What US3377006 described is to synthesize the Y zeolite with special thin native partially powder.Described at US4493902 and in same microballoon, to have contained metakaolin and high soil and crystal seed synthetic zeolite content simultaneously and be higher than 40% crystallization product.It is raw material that CN1334142A has described with kaolin, and the synthetic crystallization degree is 40～90% NaY molecular sieve under alkali condition.It is the method for feedstock production all-white clay catalyst for fluid catalytic cracking with kaolin that CN1232862A discloses a kind of.CN1105647A discloses a kind of method of utilizing bentonite for the synthetic Y zeolite of raw material.
Summary of the invention
One of purpose of the present invention provides a kind ofly utilizes cheap natural attapulgite clay to be raw material, prepares zeolite content and silica alumina ratio is all higher, the method for the crystallization product that crystallite dimension is less by in-situ crystallization; Two of purpose provides a kind of preparation method of olefinic hydrocarbon expelling catalyzer of full white-clay type.
Realize technical scheme of the present invention: the natural attapulgite clay is obtained to change brilliant atlapulgite through sulfuric acid treatment, mediate with the solid caustic soda mixing, again by extrusion molding or the moulding of rolling former, after formed body drying, the roasting, in the presence of sodium metasilicate, directed agents, NaOH, deionized water, under certain condition, carry out the hydrothermal crystallizing reaction, remove mother liquor and be washed till pH＜10 with deionized water, promptly obtain the NaY zeolite content after the drying and silica alumina ratio is all higher, the crystallization product that crystallite dimension is less; Crystallization product is carried out the super steady processing of hydro-thermal after the ammonium sulfate exchange, adopt modifications such as rare earth chloride exchange, roasting to handle then, it is low to prepare cost, the olefinic hydrocarbon expelling catalyzer of function admirable.
The present invention relates to a kind of preparation method of full white-clay type olefinic hydrocarbon expelling catalyzer, it is characterized in that:
Preparation of catalysts may further comprise the steps:
1) with natural adobe through sulfuric acid treatment, acid etching goes out part composition and impurity, making it to generate to have changes brilliant active carclazyte, after filtration, wash, refilter, dryly must change brilliant atlapulgite, technical indicator is:
SiO
2Content 55～75wt%,
Al
2O
3Content 10～20wt%,
MgO content≤0.3wt%,
Fe
2O
3Content≤0.35wt%,
CaO content≤0.4wt%;
2) brilliant atlapulgite of the commentaries on classics that step 1) is obtained and solid caustic soda mix, add dispersant, extrusion aid and peptizing agent, rolling by extrusion molding or on the rolling former makes it into the bead of different sizes, with the bar of extrusion molding or ball drying, the roasting of rolling moulding;
3) by 2～6Na
2O: 1Al
2O
3: 4～12SiO
2: 100～240H
2The mole proportioning of O, brilliant atlapulgite is changeed in a certain amount of moulding, NaOH, sodium metasilicate, deionized water, directed agents joins in the crystallization still successively, 90～100 ℃ of hydrothermal crystallizings 16～40 hours, remove by filter mother liquor, spend deionised water to cleaning solution pH＜10, it is higher to obtain NaY zeolite content and silica alumina ratio after the drying, the crystallization product that crystallite dimension is less, with crystallization product through ion-exchanged and the super steady processing of hydro-thermal, the super steady treatment conditions of hydro-thermal are: 450～650 ℃ of treatment temperatures, processing time 0.5～4h, 50～100% circulating water steam; Prepare full white-clay type olefinic hydrocarbon expelling catalyzer;
Wherein said adobe comprises Concave-convex clay rod, bentonite, imvite;
The acid treatment condition of wherein said clay is: sulfuric acid concentration is 5～40%, and the solid-to-liquid ratio of clay and sulfuric acid is 1: 1～1: 3, and treatment temperature is 50～80 ℃, and the processing time is 3～8 hours;
The mass ratio of wherein said solid caustic soda/brilliant atlapulgite of commentaries on classics is 0.75～1.05, and dispersant is a sodium metasilicate, and extrusion aid is the sesbania powder, and peptizing agent is a deionized water, and the formed body sintering temperature is 400～850 ℃;
The mol ratio that wherein said directed agents is formed is:
12～18SiO
2∶1Al
2O
3∶10～20Na
2O∶280～350H
2O；
The wherein said crystallization product NaY zeolite content that obtains by the in-situ crystallization reaction is 50～90%, and silica alumina ratio is 4.5～5.7, and grain size is 0.1～0.5 μ m;
Wherein said ion modification reagent is selected from ammonium sulfate, rare earth chloride, ammonium phosphate, ammonium nitrate, ammonium chloride;
In the wherein said catalyst rare earth oxide content be 1～10%, sodium oxide content less than 1.5%, iron oxide content less than 0.35%, content of magnesia is less than 0.3%, calcium oxide content is less than 0.4%;
The full white-clay type olefinic hydrocarbon expelling catalyzer of wherein said preparation, reaction condition is: 150～200 ℃ of reaction temperatures, operating pressure 1.0～2.0MPa, the charging air speed is 0.5～25hr
-1
According to preparation method of the present invention, its preferred feature is:
Preparation of catalysts may further comprise the steps:
1) with natural adobe through sulfuric acid treatment, acid etching goes out part composition and impurity, making it to generate to have changes brilliant active carclazyte, after filtration, wash, refilter, dryly must change brilliant atlapulgite, technical indicator is:
SiO
2Content 60～70wt%,
Al
2O
3Content 12～18wt%,
MgO content≤0.3wt%,
Fe
2O
3Content≤0.35wt%,
CaO content≤0.4wt%;
2) brilliant atlapulgite of the commentaries on classics that step 1) is obtained and solid caustic soda mix, add dispersant, extrusion aid and peptizing agent, rolling by extrusion molding or on the rolling former makes it into the bead of different sizes, with the bar of extrusion molding or ball drying, the roasting of rolling moulding;
3) by 3～5Na
2O: 1Al
2O
3: 6～10SiO
2: 120～200H
2The mole proportioning of O, brilliant atlapulgite, NaOH, sodium metasilicate, deionized water, directed agents are changeed in a certain amount of moulding to join in the crystallization still successively, 95～100 ℃ of hydrothermal crystallizings 20～36 hours, remove by filter mother liquor, spend deionised water to cleaning solution pH＜10, it is higher to obtain NaY zeolite content and silica alumina ratio after the drying, the crystallization product that crystallite dimension is less, with crystallization product through ion-exchanged and the super steady processing of hydro-thermal, the super steady treatment conditions of hydro-thermal are: 500～600 ℃ of treatment temperatures, processing time 1～2h, 70～100% circulating water steam; Prepare full white-clay type olefinic hydrocarbon expelling catalyzer;
Wherein said adobe comprises Concave-convex clay rod, bentonite, imvite;
The acid treatment condition of wherein said clay is: sulfuric acid concentration is 10～30%, and the solid-to-liquid ratio of clay and sulfuric acid is 1: 2～1: 3, and treatment temperature is 60～70 ℃, and the processing time is 4～6 hours;
The mass ratio of wherein said solid caustic soda/brilliant atlapulgite of commentaries on classics is 0.80～0.96, and dispersant is a sodium metasilicate, and extrusion aid is the sesbania powder, and peptizing agent is a deionized water, and the formed body sintering temperature is 500～650 ℃;
The mol ratio that wherein said directed agents is formed is:
14～16SiO
2∶1Al
2O
3∶14～16Na
2O∶300～330H
2O；
The wherein said crystallization product NaY zeolite content that obtains by the in-situ crystallization reaction is 55～88%, and silica alumina ratio is 4.5～5.7, and grain size is 0.1～0.5 μ m;
Wherein said ion modification reagent is selected from ammonium sulfate, rare earth chloride, ammonium phosphate;
In the wherein said catalyst rare earth oxide content be 3～9%, sodium oxide content less than 1.5%, iron oxide content less than 0.35%, content of magnesia is less than 0.3%, calcium oxide content is less than 0.4%;
The full white-clay type olefinic hydrocarbon expelling catalyzer of wherein said preparation, reaction condition is: 160～180 ℃ of reaction temperatures, operating pressure 1.1～1.5MPa, the charging air speed is 5～20hr
-1
The concrete method for preparing catalyst of the present invention is as follows:
One, the preparation of NaY molecular sieve
Preparation process is followed successively by:
1. the recessed soil that will cross 200 mesh sieves obtains changeing brilliant atlapulgite through sulfuric acid treatment, and the acid treatment condition is: sulfuric acid concentration is 10～30%, and the solid-to-liquid ratio of recessed soil and sulfuric acid is 1: 1～1: 3, and treatment temperature is 60～70 ℃, and the processing time is 4～6 hours.
2. will change brilliant atlapulgite and solid caustic soda is 0.80～0.96 mixing by alkali/native mass ratio, add dispersant, extrusion aid and peptizing agent, by extrusion molding or on the rolling former rolling balling, with the bar of extrusion molding or ball drying, the roasting of rolling moulding.
3. by 3～5Na
2O: 1Al
2O
3: 6～10SiO
2: 120～200H
2The proportioning of O, brilliant atlapulgite, NaOH, sodium metasilicate, deionized water, directed agents are changeed in a certain amount of moulding to join in the crystallization still successively, 95～100 ℃ of hydrothermal crystallizings 20～36 hours, remove by filter mother liquor, spend deionised water to cleaning solution pH＜10, obtain NaY zeolite content 50～90% after the drying, the zeolite silica alumina ratio is 4.5～5.7, grain size is the crystallization product of 0.1～0.5 μ m
SiO in the recessed soil of the described activity of step 1
2Content will be higher than 60%, Al
2O
3Content is greater than 12%, and MgO content is lower than 6.3%, Fe
2O
3Content is lower than content 9.0%, and CaO content is lower than 1.3%;
Described dispersant of step 2 and binding agent are selected from sodium metasilicate, NaOH, sesbania powder, methylcellulose, sodium carboxymethylcellulose etc., and addition is to be no more than 5% of recessed soil.
The mol ratio that the described directed agents of step 3 is formed is: 14～16SiO
2: 1Al
2O
3: 14～16Na
2O: 300～330H
2O.
Two, Preparation of catalysts
Preparation of catalysts is through three friendships, two roastings, and detailed process is followed successively by:
1. one hand over: add NaY molecular sieve crystallization product and the ammonium sulfate that utilizes the preparation of atlapulgite in-situ crystallization successively, the part by weight of pressing crystallization product/ammonium sulfate=2～5 adds ammonium sulfate, in the pH value is 3.0～3.5, temperature is 90 ℃ of exchanges 1 hour, exchange back microballoon after filtration, wash, refilter, one hand over material.
2. two hand over: handing over material once more with the ammonium sulfate exchange with one, hand over the part by weight of material/ammonium sulfate=2～5 to add ammonium sulfate by one, is 3.0～3.5 in pH value, and temperature is 90 ℃ of exchanges 1 hour, exchange back microballoon after filtration, wash, refilter, two friendships are expected.
3. a roasting a: roasting: hand over material roasting 1～2 hour under 550～600 ℃, 70～100% circulating water steam with two, a roasting material.
4. three hand over: a roasting material is pressed RE with mixed chlorinated rare earth
2O
3/ one roasting material=1～10% is 3.5～4.0 in pH value, temperature is to exchange 1 hour again under 90 ℃ of conditions, after the exchange after filtration, wash, refilter, three hand over and expect,
5. two roastings: three friendship material 600～650 ℃ of following roastings 2～4 hours, are got finished catalyst.
The catalyst that makes as stated above contains NaY zeolite 50～90%, and rare earth oxide content is 3～9%, and sodium oxide content is less than 1.5%, and content of magnesia is less than 0.3%, and iron oxide content is less than 0.35%, and calcium oxide content is less than 0.4%.
Technical advantage of the present invention is: utilized the recessed soil of 200 mesh sieves to be feedstock production abrasion index less crystallization product and catalyst through the brilliant atlapulgite of sulfuric acid treatment acquisition commentaries on classics; The inventive method can prepare the crystallization product that the NaY zeolite content is 50～90% (most of more than 70%).Utilize the molecular sieve of in-situ crystallization technology preparation to be evenly distributed on microballoon outer surface and duct inner surface, produce catalyst with binder method and compare, the utilization rate of molecular sieve greatly improves; In the crystallization process, molecular sieve links to each other with chemical bond with carrier, has good structural stability in position, the activity stability height.Simultaneously, because the atlapulgite cost is lower, price is far below waterglass, chemical reagent such as aluminium hydroxide, and not only serviceability is good to make the full white-clay type olefinic hydrocarbon expelling catalyzer of this method preparation, and production cost is lower.
The specific embodiment:
Embodiment 1-embodiment 5 is the preparation of crystallization product.
Embodiment 1,
Getting 400g (butt) particle is 200 purpose Concave-convex clay rods, join 800g concentration and be in 20% the sulfuric acid solution, under 60 ℃ of conditions, handled 4 hours, after filtration, washing, must change brilliant atlapulgite after the oven dry, with 288g solid caustic soda (purity is 99%), 10.32g sesbania powder mixing the rolling moulding make to become particle diameter in the bead be that 0.30～0.50 millimeter bead content is 25 (quality) %, the bead content that particle diameter is 0.50～0.70 millimeter is 60 (quality) %, the content of 0.70～1.00 millimeter bead of particle diameter is 12 quality %, and particle diameter is 3 (quality) % greater than 1 millimeter bead.At 120 ℃ of oven dry 12h, 550 ℃ of roasting 2h (down together), detect chemical composition with the x-ray fluorescence diffraction, wherein silica content is 64.87%, alumina content is 17.46%, iron oxide content is 0.33%, content of magnesia is 0.28%, calcium oxide content is 0.36%.Successively sodium silicate solution (is contained 26.45% SiO at stirring condition
2, 7.68% Na2
O) 675ml, alkali lye (containing 25% NaOH) 187.5ml, directed agents (contain 11.65%SiO
2, 1.32% Al
2O
3, 12.89 Na
2O) 43.6.5ml, deionized water 160ml and active recessed native microballoon 500g drop in the 2L stainless steel cauldron, are warmed up to 100 ℃ and thermostatic crystallization 24 hours.Crystallization removes by filter mother liquor after finishing, and washing, drying obtain the microballoon crystallization product.Contain 58% NaY molecular sieve in X-ray diffraction mensuration crystallization product, it is 4.68 that x-ray fluorescence is measured the molecular sieve silica alumina ratio.
Embodiment 2,
All reaction raw materials are with example 1, wherein acid treatment condition is for getting the recessed soil of 400g, the concentration that joins 1200g is in 20% the sulfuric acid solution, under 60 ℃ of conditions, handled 6 hours, after filtration, washing, must change brilliant atlapulgite after the oven dry, with 306g solid caustic soda (purity is 99%), 10.59g the sodium carboxymethylcellulose mixing rolls into the bead of different sizes on bowling machine, at 120 ℃ of oven dry 12h, 650 ℃ of roasting 2h, detect chemical composition with the x-ray fluorescence diffraction, wherein silica content is 65.94%, alumina content is 17.79%, iron oxide content is 0.29%, content of magnesia is 0.24%, and calcium oxide content is 0.35%.Under stirring condition successively with sodium metasilicate 795ml, alkali lye 290ml, directed agents 104.6ml, deionized water 150ml and activate recessed native microballoon 500g and drop in the 2L stainless steel cauldron, stir a period of time, thermostatic crystallization is after 28 hours in 100 ℃ of baking ovens, contain 65% NaY molecular sieve in X-ray diffraction mensuration crystallization product, it is 5.45 that x-ray fluorescence is measured its silica alumina ratio.
Embodiment 3,
All reaction raw materials are with example 1, wherein acid treatment condition is for getting the recessed soil of 400g, join 800g concentration and be in 20% the sulfuric acid solution, under 70 ℃ of conditions, handled 5 hours, after filtration, washing, must change brilliant atlapulgite after the oven dry, with 324g solid caustic soda (purity is 99%), 10.86g sesbania powder mixing rolls into the bead of different sizes on bowling machine, at 120 ℃ of oven dry 12h, 550 ℃ of roasting 2h, detect chemical composition with the x-ray fluorescence diffraction, wherein silica content is 65.77%, alumina content is 17.52%, iron oxide content is 0.26%, content of magnesia is 0.21%, and calcium oxide content is 0.32%.Under stirring condition successively with sodium metasilicate 750ml, alkali lye 267ml, directed agents 87.2ml, deionized water 168ml and activate recessed native microballoon 500g and drop in the 2L stainless steel cauldron, be warming up to 95 ℃ and thermostatic crystallization after 28 hours, contain 70% NaY molecular sieve in X-ray diffraction mensuration crystallization product, it is 5.38 that x-ray fluorescence is measured its silica alumina ratio.
Embodiment 4,
All reaction raw materials are with example 1, wherein acid treatment condition is for getting the recessed soil of 400g, the concentration that joins 800g is in 30% the sulfuric acid solution 70 ℃, handled 6 hours, after filtration, washing, must change brilliant atlapulgite after the oven dry, with 338.4g solid caustic soda (purity is 99%), 11.08g the sodium carboxymethylcellulose mixing rolls into the bead of different sizes on bowling machine, at 120 ℃ of oven dry 12h, 650 ℃ of roasting 2h, detect chemical composition with the x-ray fluorescence diffraction, wherein silica content is 65.97%, alumina content is 17.32%, iron oxide content is 0.22%, content of magnesia is 0.18%, and calcium oxide content is 0.27%.Successively sodium metasilicate 870ml, alkali lye 270ml, directed agents 122ml, deionized water 150ml, the recessed native microballoon 500g of activation are dropped in the 2L reactor, stir a period of time, thermostatic crystallization is after 34 hours in 100 ℃ of baking ovens, contain 75% NaY molecular sieve in X-ray diffraction mensuration crystallization product, it is 5.64 that x-ray fluorescence is measured its silica alumina ratio.
Embodiment 5,
All reaction raw materials and sulfuric acid treatment condition are with example 4, get 200g and change brilliant atlapulgite and 169.2g solid caustic soda (purity is 99%), 5.5g sesbania powder mixing, the silicon sol solution that in mixture, adds 276g (mass concentration is 12.5%), be extruded into Φ 1.6 bar shapeds after fully mediating evenly, at 120 ℃ of oven dry 12h, 550 ℃ of roasting 4h.After 435ml sodium metasilicate, 130ml alkali lye, 66ml directed agents, 80ml deionized water mixed in glass reactor, get 200g and activate recessed native microballoon adding wherein, thermostatic crystallization is after 34 hours in 100 ℃ of baking ovens, contain 73% NaY molecular sieve in X-ray diffraction mensuration crystallization product, it is 5.58 that x-ray fluorescence is measured its silica alumina ratio.
Embodiment 6-embodiment 10 is a Preparation of catalysts.
Embodiment 6,
(1) one hands over: add the 2kg deionized water in glass reactor, ratio in crystallization product/ammonium sulfate=2 adds 200g ammonium sulfate, after the ammonium sulfate dissolving is treated in stirring, the crystallization product 400g that adds example 1 preparation, under pH=3.5,90 ℃ of conditions, exchange 1 hour, remove by filter mother liquor, wash, refilter, get one and hand over material.
(2) two hand over: the same friendship of switching method, in the ratio of friendship material/ammonium sulfate=4, after adding 100g ammonium sulfate dissolved, adding one was handed over and is expected, exchanged 1 hour under pH=3.5,90 ℃ of conditions, removed by filter mother liquor, washes, refiltered, and got two friendship material.
(3) one roastings: hand over material roasting 2 hours under 550 ℃, 70% circulating water steam with two, a roasting material.
(4) three hand over: a roasting is expected with containing 13.2gRECl
31 (RE of mixed chlorinated rare earth solution exchange
2O
3/ one roasting material weight content is 3%), the same step of exchange process and condition (1), the exchange product after filtration, wash, refilter, three hand over material.
(5) two roastings: three friendship material 600 ℃ of roastings 2 hours, are got catalyst A.
Embodiment 7,
The crystallization product of example 2 methods preparations is prepared catalyst by the method for example 6, wherein two hand over by one and hand over the ratios of material/ammonium sulfate=5,90 ℃ of exchanges 2 hours, one baked under 100% circulating water steam roasting 2 hours, RE during three friendships
2O
3/ one roasting material weight content is 5%, gets catalyst B.
Embodiment 8,
The crystallization product of example 3 methods preparations is prepared catalyst by the method for example 7, wherein three RE when handing over
2O
3/ one roasting material weight content is that 7%, two roasting condition is 650 ℃ of roastings 2 hours, gets catalyst C.
Embodiment 9,
The crystallization product of example 4 methods preparations is prepared catalyst by the method for example 7, wherein three RE when handing over
2O
3/ one roasting material weight content is 9%, gets catalyst D.
Embodiment 10,
The crystallization product of example 5 methods preparations is prepared catalyst by the method for example 8, wherein a roasting and two roastings all directly adopt solid content be 50～60% two hand over material and three to hand over to expect 550 ℃ and 650 ℃ of roastings 4 hours, get catalyst E.
The physicochemical property of table 1 catalyst
Comparative Examples 1,
Prepare Comparative Examples 1 by the CN101433856A disclosed method;
Get 120g (pressing butt calculates) NH
4Y molecular sieve and boehmite are (with Al
2O
3Meter 37g, the CNOOC Tianjin Chemical Research ﹠ Desing Inst is produced, trade names are A201), 27.7gLa
2O
3, 4.6g sesbania powder mixes;
In mixture, add the 140ml dilute nitric acid solution, be extruded into the bar shaped of Φ 1.6 after mixing;
Above catalyst in 550 ℃ of roastings 4 hours, is obtained the comparative catalyst.
Application examples,
The laboratory activity rating condition of catalyst is as follows: strip catalyst is levigate, sieve is got 5 grams, 20～40 purpose catalyst (spheric catalyst is kept intact) and is packed into 20ml assessing reactor stage casing, and load with quartz sand or inertia alumina balls at reactor bottom and top.Feedstock oil is provided by middle extra large refinery Huizhou oil refining branch company, and the bromine index of feedstock oil is 862.8mgBr/100g, and density is 0.878g/ml.In reaction temperature is 170 ℃, and reaction pressure is 1.2Mpa, and the reaction weight space velocity is 10hr
-1Under the condition, investigate life of catalyst.The catalyst life time representation of catalysqt deactivation (bromine index of reactor outlet material is greater than 100mgBr/100g).And under condition same as described above, estimate the activity of prepared catalyst in the Comparative Examples, in contrast, measure bromine index and the results are shown in Table 2.
Table 2 different catalysts deolefination ability is investigated
Claims (2)
1. the preparation method of a full white-clay type olefinic hydrocarbon expelling catalyzer is characterized in that:
Preparation of catalysts may further comprise the steps:
1) with natural adobe through sulfuric acid treatment, acid etching goes out part composition and impurity, making it to generate to have changes brilliant active carclazyte, after filtration, wash, refilter, dryly must change brilliant atlapulgite, technical indicator is:
SiO
2Content 55～75wt%,
Al
2O
3Content 10～20wt%,
MgO content≤0.3wt%,
Fe
2O
3Content≤0.35wt%,
CaO content≤0.4wt%;
2) brilliant atlapulgite of the commentaries on classics that step 1) is obtained and solid caustic soda mix, add dispersant, extrusion aid and peptizing agent, rolling by extrusion molding or on the rolling former makes it into the bead of different sizes, with the bar of extrusion molding or ball drying, the roasting of rolling moulding;
3) by 2～6Na
2O: 1Al
2O
3: 4～12SiO
2: 100～240H
2The mole proportioning of O, brilliant atlapulgite is changeed in a certain amount of moulding, NaOH, sodium metasilicate, deionized water, directed agents joins in the crystallization still successively, 90～100 ℃ of hydrothermal crystallizings 16～40 hours, remove by filter mother liquor, spend deionised water to cleaning solution pH＜10, it is higher to obtain NaY zeolite content and silica alumina ratio after the drying, the crystallization product that crystallite dimension is less, with crystallization product through ion-exchanged and the super steady processing of hydro-thermal, the super steady treatment conditions of hydro-thermal are: 450～650 ℃ of treatment temperatures, processing time 0.5～4h, 50～100% circulating water steam; Prepare full white-clay type olefinic hydrocarbon expelling catalyzer;
Wherein said adobe comprises Concave-convex clay rod, bentonite, imvite;
The acid treatment condition of wherein said clay is: sulfuric acid concentration is 5～40%, and the solid-to-liquid ratio of clay and sulfuric acid is 1: 1～1: 3, and treatment temperature is 50～80 ℃, and the processing time is 3～8 hours;
The mass ratio of wherein said solid caustic soda/brilliant atlapulgite of commentaries on classics is 0.75～1.05, and dispersant is a sodium metasilicate, and extrusion aid is the sesbania powder, and peptizing agent is a deionized water, and the formed body sintering temperature is 400～850 ℃;
The mol ratio that wherein said directed agents is formed is:
12～18SiO
2∶1Al
2O
3∶10～20Na
2O∶280～350H
2O；
The wherein said crystallization product NaY zeolite content that obtains by the in-situ crystallization reaction is 50～90%, and silica alumina ratio is 4.5～5.7, and grain size is 0.1～0.5 μ m;
Wherein said ion modification reagent is selected from ammonium sulfate, rare earth chloride, ammonium phosphate, ammonium nitrate, ammonium chloride;
In the wherein said catalyst rare earth oxide content be 1～10%, sodium oxide content less than 1.5%, iron oxide content less than 0.35%, content of magnesia is less than 0.3%, calcium oxide content is less than 0.4%;
The full white-clay type olefinic hydrocarbon expelling catalyzer of wherein said preparation, reaction condition is: 150～200 ℃ of reaction temperatures, operating pressure 1.0～2.0MPa, the charging air speed is 0.5～25hr
-1
2. according to the described preparation method of claim 1, it is characterized in that:
Preparation of catalysts may further comprise the steps:
1) with natural adobe through sulfuric acid treatment, acid etching goes out part composition and impurity, making it to generate to have changes brilliant active carclazyte, after filtration, wash, refilter, dryly must change brilliant atlapulgite, technical indicator is:
SiO
2Content 60～70wt%,
Al
2O
3Content 12～18wt%,
MgO content≤0.3wt%,
Fe
2O
3Content≤0.35wt%,
CaO content≤0.4wt%;
2) brilliant atlapulgite of the commentaries on classics that step 1) is obtained and solid caustic soda mix, add dispersant, extrusion aid and peptizing agent, rolling by extrusion molding or on the rolling former makes it into the bead of different sizes, with the bar of extrusion molding or ball drying, the roasting of rolling moulding;
3) by 3～5Na
2O: 1Al
2O
3: 6～10SiO
2: 120～200H
2The mole proportioning of O, brilliant atlapulgite, NaOH, sodium metasilicate, deionized water, directed agents are changeed in a certain amount of moulding to join in the crystallization still successively, 95～100 ℃ of hydrothermal crystallizings 20～36 hours, remove by filter mother liquor, spend deionised water to cleaning solution pH＜10, it is higher to obtain NaY zeolite content and silica alumina ratio after the drying, the crystallization product that crystallite dimension is less, with crystallization product through ion-exchanged and the super steady processing of hydro-thermal, the super steady treatment conditions of hydro-thermal are: 500～600 ℃ of treatment temperatures, processing time 1～2h, 70～100% circulating water steam; Prepare full white-clay type olefinic hydrocarbon expelling catalyzer;
Wherein said adobe comprises Concave-convex clay rod, bentonite, imvite;
The acid treatment condition of wherein said clay is: sulfuric acid concentration is 10～30%, and the solid-to-liquid ratio of clay and sulfuric acid is 1: 2～1: 3, and treatment temperature is 60～70 ℃, and the processing time is 4～6 hours;
The mass ratio of wherein said solid caustic soda/brilliant atlapulgite of commentaries on classics is 0.80～0.96, and dispersant is a sodium metasilicate, and extrusion aid is the sesbania powder, and peptizing agent is a deionized water, and the formed body sintering temperature is 500～650 ℃;
The mol ratio that wherein said directed agents is formed is:
14～16SiO
2∶1Al
2O
3∶14～16Na
2O∶300～330H
2O；
The wherein said crystallization product NaY zeolite content that obtains by the in-situ crystallization reaction is 55～88%, and silica alumina ratio is 4.5～5.7, and grain size is 0.1～0.5 μ m;
Wherein said ion modification reagent is selected from ammonium sulfate, rare earth chloride, ammonium phosphate;
In the wherein said catalyst rare earth oxide content be 3～9%, sodium oxide content less than 1.5%, iron oxide content less than 0.35%, content of magnesia is less than 0.3%, calcium oxide content is less than 0.4%;
The full white-clay type olefinic hydrocarbon expelling catalyzer of wherein said preparation, reaction condition is: 160～180 ℃ of reaction temperatures, operating pressure 1.1～1.5MPa, the charging air speed is 5～20hr
-1
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103230809A (en) * | 2013-04-16 | 2013-08-07 | 中国海洋石油总公司 | Kaolinic heavy aromatic hydrocarbon transalkylation catalyst preparation method |
| CN104163437A (en) * | 2014-09-03 | 2014-11-26 | 中国海洋石油总公司 | Preparation method of integral NaY molecular sieve |
| CN105536875A (en) * | 2016-01-22 | 2016-05-04 | 张玲 | Preparation method of carclazyte catalyst of deolefin |
| CN114425427A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Aromatic hydrocarbon olefin removal catalyst and preparation method and application thereof |
| CN116371459A (en) * | 2023-06-02 | 2023-07-04 | 潍坊正轩稀土催化材料有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN117046510A (en) * | 2023-10-11 | 2023-11-14 | 煜安特(山东)环保科技有限公司 | Fatlute pyrolysis catalyst and preparation method thereof |
| CN117899842A (en) * | 2023-12-25 | 2024-04-19 | 南京工业大学 | Preparation method of hydrophobic VOCs adsorbent NaY-MCM-41 |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4493902A (en) * | 1983-02-25 | 1985-01-15 | Engelhard Corporation | Fluid catalytic cracking catalyst comprising microspheres containing more than about 40 percent by weight Y-faujasite and methods for making |
| CN1317547A (en) * | 2000-04-07 | 2001-10-17 | 中国石油天然气股份有限公司兰州炼化分公司 | FCC catalyst for reducing olefin content in gasoline and its preparing process |
| CN1334142A (en) * | 2000-07-19 | 2002-02-06 | 中国石油天然气股份有限公司兰州炼化分公司 | Process for synthesizing molecular sieve from gaolin |
| US6500996B1 (en) * | 1999-10-28 | 2002-12-31 | Exxonmobil Oil Corporation | Process for BTX purification |
-
2010
- 2010-11-09 CN CN 201010539508 patent/CN102091648B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4493902A (en) * | 1983-02-25 | 1985-01-15 | Engelhard Corporation | Fluid catalytic cracking catalyst comprising microspheres containing more than about 40 percent by weight Y-faujasite and methods for making |
| US6500996B1 (en) * | 1999-10-28 | 2002-12-31 | Exxonmobil Oil Corporation | Process for BTX purification |
| CN1317547A (en) * | 2000-04-07 | 2001-10-17 | 中国石油天然气股份有限公司兰州炼化分公司 | FCC catalyst for reducing olefin content in gasoline and its preparing process |
| CN1334142A (en) * | 2000-07-19 | 2002-02-06 | 中国石油天然气股份有限公司兰州炼化分公司 | Process for synthesizing molecular sieve from gaolin |
Cited By (11)
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|---|---|---|---|---|
| CN103230809A (en) * | 2013-04-16 | 2013-08-07 | 中国海洋石油总公司 | Kaolinic heavy aromatic hydrocarbon transalkylation catalyst preparation method |
| CN103230809B (en) * | 2013-04-16 | 2015-03-18 | 中国海洋石油总公司 | Kaolinic heavy aromatic hydrocarbon transalkylation catalyst preparation method |
| CN104163437A (en) * | 2014-09-03 | 2014-11-26 | 中国海洋石油总公司 | Preparation method of integral NaY molecular sieve |
| CN105536875A (en) * | 2016-01-22 | 2016-05-04 | 张玲 | Preparation method of carclazyte catalyst of deolefin |
| CN114425427A (en) * | 2020-10-10 | 2022-05-03 | 中国石油化工股份有限公司 | Aromatic hydrocarbon olefin removal catalyst and preparation method and application thereof |
| CN114425427B (en) * | 2020-10-10 | 2023-08-04 | 中国石油化工股份有限公司 | Aromatic hydrocarbon olefin removal catalyst and preparation method and application thereof |
| CN116371459A (en) * | 2023-06-02 | 2023-07-04 | 潍坊正轩稀土催化材料有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN116371459B (en) * | 2023-06-02 | 2023-08-11 | 潍坊正轩稀土催化材料有限公司 | Catalytic cracking catalyst and preparation method thereof |
| CN117046510A (en) * | 2023-10-11 | 2023-11-14 | 煜安特(山东)环保科技有限公司 | Fatlute pyrolysis catalyst and preparation method thereof |
| CN117046510B (en) * | 2023-10-11 | 2024-01-05 | 煜安特(山东)环保科技有限公司 | Fatlute pyrolysis catalyst and preparation method thereof |
| CN117899842A (en) * | 2023-12-25 | 2024-04-19 | 南京工业大学 | Preparation method of hydrophobic VOCs adsorbent NaY-MCM-41 |
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