CN1062331A - Improved the preparation of tart cross-linked clay - Google Patents
Improved the preparation of tart cross-linked clay Download PDFInfo
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- CN1062331A CN1062331A CN 90109798 CN90109798A CN1062331A CN 1062331 A CN1062331 A CN 1062331A CN 90109798 CN90109798 CN 90109798 CN 90109798 A CN90109798 A CN 90109798A CN 1062331 A CN1062331 A CN 1062331A
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Abstract
A kind of preparation method of molecular sieve of layered crosslinking clay column comprises the crosslinking reaction of laminated clay and fluorine-containing inorganic metal hydroxy polymer, aging, washing, drying and other steps.Laminated clay can be the smectite class clay of single-storeyed mineral structure, also can be the clay with regular interbed mineral structure.The inorganic metal hydroxy polymer can be the hydroxy polymer of metals such as chromium, zirconium, aluminium, cobalt, iron.The cross-linked clay that adopts this method to prepare not only has the same macroporous structure of preparing with ordinary method of cross-linked clay, and has the acidity stronger than the latter, higher acid amount and acid site thermostability, can be used for the hydrocarbon conversion reaction of solid acid catalysis.
Description
The invention relates to a kind of preparation method of molecular sieve of layered crosslinking clay column.Exactly, be a kind of about having preparation method than peracid amount and strength of acid, fluorine-containing molecular sieve of layered crosslinking clay column.
Molecular sieve of layered crosslinking clay column is the product that laminated clay and linking agent make by crosslinking reaction.Laminated clay is meant that those itself contain or contain after treatment the swelling type clay of commutative interlayer cation.Linking agent can be organically, also can be inorganic.Organic crosslinking agent generally is the dication of triethylene diamine, siliceous organic cation etc.Inorganic crosslinking agent generally is the hydroxy polymer of metals such as zirconium, aluminium, chromium, titanium, nickel, iron, zinc or by more than one are formed among them multipolymer or mixture.
Owing to have stronger thermostability and acidity than the molecular sieve of layered crosslinking clay column made from organic crosslinking agent with inorganic crosslinking agent, therefore the product that people's research, being mostly of using are made with inorganic crosslinking agent, the aluminium cross-linked clay seam column molecular sieve made from aluminum crosslinker for example, but the acid amount of these molecular sieve of layered crosslinking clay column is limited, and the acid site mainly concentrates on the weak acid part, and the acid site of for example aluminium cross-linked clay seam column molecular sieve mainly concentrates on-3.0＜Ho＜3.3 scopes.
According to reported in literature, improving cross-linked clay tart method has following a few class:
The method that adds water: reported on the CN86104720 water or its Equivalent are added to method on the cross-linked clay.Though this method makes moderate progress to the acidity of cross-linked clay, it only is the method that can adopt when using cross-linked clay or contain the catalyzer of cross-linked clay.
Improve the method for raw material laminated clay: USP3,976,744 and J.Catal., when once having reported synthetic laminated clay in 86,1～8,1984 with metal, for example nickel is introduced in the alumina octahedral sheet of native flaggy, thereby has improved the acidity of the catalyzer that contains this laminated clay.Clays and Clay Minerals 33(2), has reported polynite and oxyaluminum crosslinked polymer after handling with NH4F in 89～98,1985, and the acidity and the catalytic activity of products obtained therefrom all improve to some extent.Clays and Clay Minerals, 33(2), in 99～107,1985 then report adopt fluorine hectorite (fluorhectorites) and oxyaluminum crosslinked polymer, the acidity of products obtained therefrom and catalytic activity can be improved.
The method of load SO4: reported on the CN1043270A with the vitriolic ammonium salt and handled cross-linked clay, carried out the method for roasting then, thereby acid amount, strength of acid and the catalytic activity of cross-linked clay are greatly improved.But it is the cross-linked clay of pillar that this method only limits to zirconium, titanium, iron, tin.
Except that above-mentioned three class methods, Shang Weijian improves cross-linked clay tart report by linking agent.Though Mineral Pol. 13(2), has reported on 15～20,1982 with fluoro oxyaluminum (fluorohydroxyaluminium) and the crosslinked method of polynite, its objective is the thermostability of product is improved.
The object of the present invention is to provide and a kind ofly improve the method that the cross-linked clay tart prepares cross-linked clay by changing linking agent.
Method provided by the invention is: with fluorine-containing inorganic metal hydroxy polymer is that linking agent and laminated clay carry out crosslinking reaction, thereby makes the cross-linked clay with peracid amount, high strength of acid and stable acid site, and concrete steps are as follows:
(1) preparation of clay slurry: the calcium type laminated clay that will remove mechanical impurity is modified as sodium type or ammonium type with ion-exchange techniques, makes the heavy % in solid content＜5, particle diameter≤2 micron clay slurry;
(2) preparation of cross-linking agent solution: in inorganic metal hydroxy polymer solution, add a certain amount of fluorochemical, make that the mol ratio of fluorine and metal ion in the solution is 0.5～2.5, the concentration of metal ion is 0.03～0.2 mole, left standstill under the room temperature aging 2～7 days;
(3) crosslinking reaction: with the feed ratio of every gram soil clay slurry is added in the fluorine-containing cross-linking agent solution, under agitation more than 2 hours, control the PH of slurries 2～4 with dilute hydrochloric acid during reaction in room temperature reaction with the linking agent of 0.6～6.0 mmole metal ion;
(4) aging, washing, drying: continue to keep slurries PH2～4, at room temperature left standstill aging 4～24 hours, filter, be washed till no Cl with deionized water
-, 100～120 ℃ of dryings.
Said laminated clay can be the single-storeyed mineral structure that has of natural or synthetic among the present invention, basal spacing (d001) is the smectite class clay of 0.9～1.5 nanometer, if you would take off soil, wilkinite, Hunk takes off stone, beidellite, vermiculite etc., also can be the regular interbed mineral structure of having of natural or synthetic (promptly rearranging) by two kinds of individual layer mineral clay component rule interleaved, the clay of basal spacing (d001) 〉=1.7 nanometer, as mica-smectite (as rectorite leng), illite-smectite, glaukonine-smectite, chlorite-smectite, mica-vermiculite, kaolin-smectites etc. can also be other clay mixtures that contains in the above-mentioned clay one or more.
The present invention said inorganic metal hydroxy polymer is meant and is commonly used for linking agent, as the hydroxy polymer of metals such as chromium, zirconium, aluminium, iron, cobalt, or the multipolymer or the mixture of more than one compositions in the above-mentioned metal.They all can adopt various known technologies to make, described in for example following document: Yamanaka S.and Brindley G.W., Clays and Clay Minerals, 27,119,1979; Lahav N., Shani U.and Shabtai J., Clays and Clay Minerals, 26,107,1978; Brindley G.W.and Yamanaka S, American Mineralogist, 64,830～835,1979; Charles F.Bass Jr.and Robert E.Mesmer, The Hydrolysis of Cations, John Wiley ﹠amp; Sons, New York, 1976, P226～237.
Said fluorochemical is meant Sodium Fluoride or Neutral ammonium fluoride among the present invention.
Method provided by the present invention is applicable to the cross-linked clay of multiple linking agent preparation.The cross-linked clay that adopts method provided by the present invention to make not only has the same macroporous structure of preparing with ordinary method of cross-linked clay, and have the acidity stronger, higher acid amount and an acid site thermostability than the latter, be applicable to all kinds of hydrocarbon conversion reactions of solid acid catalysis, as cracking, isomerization, alkylation etc.
Following example will give further instruction to method provided by the present invention.
Example 1～4
Prepare cross-linked clay with fluorine-containing chromium cross linker by method provided by the invention.
(1) natural accumulation supporting stone (belonging to regular interbed mineral clay) and wilkinite (belonging to the individual layer mineral clay) are mixed for 3 kilograms with strongly acidic styrene's sodium type ion exchange resin of 20 kilograms of deionized waters and exchange capacity 4 milligramequivalent/grams respectively for each 1 kilogram, stirred 24 hours, left standstill 7 hours, take out the clay slurry (this part clay particle diameter≤2 microns) on 10 centimetres on upper strata, record its solid content and be respectively 2.7 heavy % and 5.0 heavy %.
(2) with proper C rCl36H
2O(Beijing Chemical Plant product, chemical pure) being dissolved in deionized water makes the certain density aqueous solution, adds a certain amount of NaOH and NaF then, leaving standstill the aging fluorine-containing hydroxyl polymeric chromium chloride linking agent that promptly gets under the room temperature.
(3) by certain feed ratio clay slurry is joined in the chromium cross linker, stirring reaction at room temperature simultaneously with PH2～4 of the hydrochloric acid soln control slurries of 4.0 heavy %, leaves standstill agingly, filters, and washing is to there not being Cl
-, 100～120 ℃ are drying to obtain the cross-linked clay product.
Each routine operating parameters is listed in table 1.
Example 5
Prepare cross-linked clay with fluorine-containing zirconium crosslink agent by method provided by the invention.
(1) according to step (1) preparation rectorite leng slurries in the example 1～4.
(2) with ZrOCl28H2O(Beijing Chemical Plant product, chemical pure) being dissolved in deionized water, to make concentration be 0.3 mole the aqueous solution, add a certain amount of NaF then and make F
-/ Zr
4+Mol ratio is 1.5, with deionized water it is diluted to Zr then
4+Concentration is 0.1 mole, leaves standstill under the room temperature aging 5 days, promptly gets fluorine-containing hydroxyl polymeric zirconium chloride linking agent.
(3) feed ratio by 3.6 mmoles zirconium/gram soil adds the rectorite leng slurries in the zirconium crosslink agent, and at room temperature stirring reaction is 4 hours, and reaction time control slurrying liquid PH2～4 keep this PH at room temperature to leave standstill aging 8 hours, filter, and washing is to there not being Cl
-, drying, it is tired promptly to get cross-linked clay F-Zr-.
Example 6
Prepare cross-linked clay with fluorine-containing aluminum crosslinker by method provided by the invention.
(1) according to step (1) preparation bentonite slurry in the example 1～4.
(2) with AlCl36H2O(Beijing Chemical Plant product, chemical pure) being dissolved in deionized water, to make concentration be 0.26 mole the aqueous solution, adds a certain amount of NaOH solution and NaF then, makes OH
-/ Al
3+And F
-/ Al
3+Mol ratio is respectively 1.5 and 0.65, with deionized water it is diluted to Al then
3+Concentration is 0.066 mole, leaves standstill under the room temperature aging 7 days, promptly gets fluorine-containing hydroxyl polymeric aluminum chloride linking agent.
(3) feed ratio by 6.0 mmoles aluminium/gram soil adds bentonite slurry in the aluminum crosslinker, and according to the conditioned response described in the example 5, aging, filtration, washing, drying, it is swollen promptly to get cross-linked clay F-Al-.
Example 7
Prepare cross-linked clay with fluorine-containing chromium aluminum crosslinker by method provided by the invention.
(1) according to step (1) preparation rectorite leng slurries in the example 1～4.
(2) respectively CrCl36H2O and AlCl36H2O being dissolved in deionized water, to make concentration be 0.5 mole the aqueous solution, adds a certain amount of NaOH solution then respectively, makes OH
-/ Cr
3+And OH
-/ Al
3+Mol ratio respectively does for oneself 1.5, this two solution is mixed mixed Cr
3+/ Al
3+Mol ratio is 1.0, and adding concentration is 0.5 mole NH4F solution in above-mentioned mixed solution, makes F
-/ (Cr
3++ Al
3+) mol ratio is 1.0, with deionized water it being diluted to chromium concn is 0.06 mole, leaves standstill under the room temperature aging 4 days, promptly gets fluorine-containing hydroxyl polymeric chromium chloride-aluminum crosslinker.
(3) feed ratio by 0.6 mmole chromium-aluminium/gram soil adds the rectorite leng slurries in the chromium aluminum crosslinker, and at room temperature stirring reaction is 3 hours, and reaction time control slurrying liquid PH2～4 keep this PH at room temperature to leave standstill aging 24 hours, filter, and washing is to there not being Cl
-, drying, it is tired promptly to get cross-linked clay F-Cr-Al-.
Comparative Examples
Prepare the cross-linked clay sample with not fluorine-containing linking agent method routinely.
Prepare rectorite leng and bentonite slurry respectively according to step (1) in the example 1～4.
Press step in the example 3 (2) preparation chromium cross linker, but do not add NaF.It is tired and Cr-is swollen to prepare contrast cross-linked clay sample Cr-according to the described condition of step (3) in example 3 and 4 respectively with above-mentioned not fluorine-containing chromium cross linker and rectorite leng, bentonite slurry respectively.
Press step in the example 5 (2) preparation zirconium crosslink agent, but do not add NaF.It is tired to go out to contrast cross-linked clay sample Zr-according to the described condition of step (3) in the example 5 with above-mentioned not fluorine-containing zirconium crosslink agent and rectorite leng slurry preparation.
Press step in the example 6 (2) preparation aluminum crosslinker, but do not add NaF.It is swollen to prepare contrast cross-linked clay sample Al-according to the described condition of step (3) in the example 6 with above-mentioned not fluorine-containing aluminum crosslinker and bentonite slurry.
Press step in the example 7 (2) preparation chromium-aluminum crosslinker, but do not add NH4F.It is tired to go out to contrast cross-linked clay sample Cr-Al-according to the described condition of step (3) in the example 7 with above-mentioned not fluorine-containing chromium-aluminum crosslinker and rectorite leng slurry preparation.
The content of linking agent metal in the scantlings of the structure that table 2 listed the specific surface that is recorded by low temperature N2 absorption method of above-mentioned each routine cross-linked clay sample and pore volume, recorded by x-ray diffraction method, the cross-linked clay that records by atomic absorption spectrum.
Table 2
| Cross-linked clay | Specific surface rice 2/ gram | Pore volume milliliter/gram | The bed thickness nanometer | Basal spacing d001 nanometer | Interlamellar spacing, nanometer | The heavy % of chromium, zirconium or aluminium content |
| F-Cr-tires out (III) | 178 | 0.15 | 1.96 | 2.56 | 0.60 | 1.30 |
| Cr-is tired | 165 | 0.15 | 1.96 | 2.56 | 0.60 | 1.20 |
| F-Cr-is swollen | 307 | 0.20 | 0.90 | 1.50 | 0.60 | 3.40 |
| Cr-is swollen | 298 | 0.20 | 0.90 | 1.50 | 0.60 | 3.20 |
| F-Zr-is tired | 107 | 0.11 | 1.96 | 3.96 | 2.00 | 1.09 |
| Zr-is tired | 63 | 0.08 | 1.96 | 3.96 | 2.00 | 0.99 |
| F-Al-is swollen | 305 | 0.20 | 0.90 | 1.80 | 0.90 | 4.77 |
| Al-is swollen | 295 | 0.20 | 0.90 | 1.80 | 0.90 | 4.56 |
| F-Cr-Al-is tired | 173 | 0.15 | 1.96 | 2.86 | 0.90 | / |
| Cr-Al-is tired | 168 | 0.15 | 1.96 | 2.86 | 0.90 | / |
Example 8
Have acid amount and the strength of acid that significantly improves the invention provides the cross-linked clay that cross-linked clay that method makes makes with ordinary method.
The total acid content and the strength of acid of prepared sample in example 3,4,5,6 and its corresponding Comparative Examples have been listed in the table 3.Wherein total acid content is to adsorb Differential scanning calorimetry (refining of petroleum, 1,6,1979) with ammonia to record, before sample is tested in nitrogen 350 ℃ purify 0.5 hour, adsorption temp is 350 ℃.Strength of acid records with the n-butylamine titration method.
Example 9
Has the acid site thermostability that significantly improves the invention provides the cross-linked clay that cross-linked clay that method makes makes with ordinary method.
Listed the acid site reservation degree that prepared sample records with ammonia absorption Differential scanning calorimetry in example 3,4,5,6 and its corresponding Comparative Examples in the table 4.Before sample is tested in nitrogen 350 ℃ purify 0.5 hour, inhale, desorption temperature is 350 ℃, Ho is the total acid content before the desorption, H10 is the acid amount of desorption after 10 minutes.
With the cross-linked clay F-Al-that makes in the example 6 swollen and contrast accordingly the swollen fresh sample of sample Al-and in retort furnace the aging sample of 300 ℃ of roastings after 2 hours on the normal pressure pulse micro-inverse, estimate respectively, raw material is an isopropyl benzene, each 0.3 microlitre of raw material sample size, 20～40 order cross-linked clay sample loading amounts are 0.1 gram, temperature of reaction is 300 ℃, the results are shown in Table 5.
Example 10
Has the cracking activity that significantly improves the invention provides the cross-linked clay that cross-linked clay that method makes makes with ordinary method.
With the isopropyl benzene is raw material, with example 1,2,3,5,7 and corresponding Comparative Examples in prepared sample on normal pressure pulse micro-inverse device, estimate, appreciation condition the results are shown in Table 6 with example 9.
With the normal heptane is raw material, and prepared sample in example 4,6 and the corresponding Comparative Examples thereof is estimated on normal pressure pulse micro-inverse device, and appreciation condition the results are shown in Table 7 with example 9.
Example 11
Has the alkylation activity that significantly improves the invention provides the cross-linked clay that cross-linked clay that method makes makes with ordinary method.
With the alkylated reaction of prepared sample difference catalysis laurylene and benzene in example 3,4,6 and the corresponding Comparative Examples thereof, the volume ratio of benzene and laurylene is 5: 1, and 83 ℃ of temperature of reaction, 60～80 order sample loading amounts are 1.0 grams, the results are shown in Table 8.
Claims (6)
1, a kind of preparation method of molecular sieve of layered crosslinking clay column is characterized in that it is made up of following step:
(1) calcium type laminated clay is modified as sodium type or ammonium type with ion exchange method, makes the heavy % in solid content＜5, particle diameter≤2 micron clay slurry;
(2) in the solution of inorganic metal hydroxy polymer, add a certain amount of fluorochemical, make that the mol ratio of fluorine and metal ion in the solution is 0.5～2.5, the concentration of metal ion is 0.03～0.2 mole, leave standstill under the room temperature and wore out 2～7 days;
(3) with the feed ratio of every gram soil, clay slurry is added in the fluorine-containing cross-linking agent solution, under agitation more than 2 hours, control the PH of slurries 2～4 with dilute hydrochloric acid during reaction in room temperature reaction with the linking agent of 0.6～6.0 mmole metal ion;
(4) keep PH2～4, at room temperature left standstill aging 4～24 hours, filter washing, drying.
2, according to the described preparation method of claim 1, it is characterized in that said laminated clay be natural or synthetic have single-storeyed mineral structure, basal spacing (d001) is the smectite class clay of 0.9～1.5 nanometer, or clay, or contain in the above-mentioned clay one or more other clay mixture with regular interbed mineral structure, basal spacing (d001) 〉=1.7 nanometer.
3,, it is characterized in that said clay with single-storeyed mineral structure comprises that polynite, wilkinite, Hunk take off stone, beidellite, vermiculite etc. according to the described preparation method of claim 2.
4,, it is characterized in that said clay with regular interbed mineral structure comprises mica-smectite (as: rectorite leng), illite-smectite, glaukonine-smectite, chlorite-smectite, mica-vermiculite, kaolin-smectite etc. according to the described preparation method of claim 2.
5,, it is characterized in that hydroxy polymer that said inorganic metal hydroxy polymer is chromium, zirconium, aluminium, iron, cobalt or by more than one are formed among them multipolymer or mixture according to the described preparation method of claim 1.
6,, it is characterized in that said fluorochemical is Sodium Fluoride or Neutral ammonium fluoride according to the described preparation method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90109798 CN1028289C (en) | 1990-12-13 | 1990-12-13 | Process for preparing crosslinking clay having improved acidity |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 90109798 CN1028289C (en) | 1990-12-13 | 1990-12-13 | Process for preparing crosslinking clay having improved acidity |
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| Publication Number | Publication Date |
|---|---|
| CN1062331A true CN1062331A (en) | 1992-07-01 |
| CN1028289C CN1028289C (en) | 1995-04-26 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 90109798 Expired - Fee Related CN1028289C (en) | 1990-12-13 | 1990-12-13 | Process for preparing crosslinking clay having improved acidity |
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|---|---|
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042126C (en) * | 1991-09-03 | 1999-02-17 | 环球油品公司 | Synthetic dioctahedral smectite clays |
| CN1043567C (en) * | 1993-06-17 | 1999-06-09 | 昆士兰大学 | Kaolin derivatives |
| CN103191722A (en) * | 2013-04-23 | 2013-07-10 | 江苏龙源催化剂有限公司 | Crosslinked montmorillonite honeycomb type denitration catalyst and preparation method thereof |
| CN113209539A (en) * | 2021-05-17 | 2021-08-06 | 重庆工程职业技术学院 | Coal mine composite colloid fire prevention and extinguishing material and preparation method thereof |
-
1990
- 1990-12-13 CN CN 90109798 patent/CN1028289C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1042126C (en) * | 1991-09-03 | 1999-02-17 | 环球油品公司 | Synthetic dioctahedral smectite clays |
| CN1043567C (en) * | 1993-06-17 | 1999-06-09 | 昆士兰大学 | Kaolin derivatives |
| CN103191722A (en) * | 2013-04-23 | 2013-07-10 | 江苏龙源催化剂有限公司 | Crosslinked montmorillonite honeycomb type denitration catalyst and preparation method thereof |
| CN103191722B (en) * | 2013-04-23 | 2015-03-25 | 江苏龙源催化剂有限公司 | Crosslinked montmorillonite honeycomb type denitration catalyst and preparation method thereof |
| CN113209539A (en) * | 2021-05-17 | 2021-08-06 | 重庆工程职业技术学院 | Coal mine composite colloid fire prevention and extinguishing material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1028289C (en) | 1995-04-26 |
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