CN1018817B - Process for preparing cross-linking clay with increased acidic property - Google Patents
Process for preparing cross-linking clay with increased acidic propertyInfo
- Publication number
- CN1018817B CN1018817B CN 88108611 CN88108611A CN1018817B CN 1018817 B CN1018817 B CN 1018817B CN 88108611 CN88108611 CN 88108611 CN 88108611 A CN88108611 A CN 88108611A CN 1018817 B CN1018817 B CN 1018817B
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- China
- Prior art keywords
- clay
- cross
- linking
- smectite
- described preparation
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Abstract
The present invention relates to a preparing method of cross-linking clay with increased acidic property and acidic strength, which is prepared by the following steps: after the cross-linking reaction between laminated clay and hydroxyl polymers of inorganic metals are conducted, the reaction products are treated by the ammonium salt of sulfuric acid; then the reaction products are calcined. The cross-linking clay prepared by the method not only maintains the original macroporous structure of the cross-linking clay, but also has the advantages of stronger acidic strength and higher acidic property, for example, the activity of cumene cracking reaction can be improved from original 12% to over 90%. The cross-linking clay is suitable for various hydrocarbon conversion reactions catalyzed by solid acid.
Description
The present invention is a kind of preparation method about cross-linked clay, exactly, is a kind of preparation method of the cross-linked clay about acid amount with raising and strength of acid.
Cross-linked clay 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 bentonite clay of commutative interlayer cation.Linking agent generally is that volume is big, the higher positively charged ion of electricity price, and they 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 aluminium, zirconium, chromium, titanium, nickel and zinc or by more than one are formed among them multipolymer or mixture.
Owing to have stronger thermostability and acidity than the cross-linked clay made from organic crosslinking agent with inorganic crosslinking agent, therefore being mostly of people's research, application with inorganic crosslinking agent, the cross-linked clay made from aluminum crosslinker for example, but the acid amount of these cross-linked clays is limited, and the acid site mainly concentrates on weak acid part (for example aluminium cross-linked clay mainly concentrates on-3.0＜Ho＜3.3 scopes).
In order to improve the acidity of cross-linked clay, reported on the CN86104720 water or its Equivalent have been added to method on the cross-linked clay.Though this method makes moderate progress to the acidity of cross-linked clay, but only be the method that when using cross-linked clay or contain the catalyzer of cross-linked clay, can adopt, how from the cross-linked clay preparation process, solve this problem, seldom appear in the newspapers in the document and lead from cross-linked clay itself.USP3,976,744 and J.Catal, 86,1-8, with metal, for example nickel was introduced in the alumina octahedral sheet of native flaggy, thereby had improved the acidity of the catalyzer that contains this laminated clay when once having reported synthetic laminated clay on 1984.
Reported a kind of preparation method of crosslinked regular interbed mineral clay among the CN86101990, its step is as follows:
(1) land reform of natural calcium type raw material is sodium type, ammonia type or rare-earth type, and make solid content less than 5 heavy %, the soil particle diameter is less than 2 * 10
-6The clay slurry of rice;
(2) the inorganic metal hydroxy polymer be mixed with concentration be 10～1000 milligram-atom aluminium/liter or 50～100 milligram-atom zirconiums/liter the aqueous solution;
(3) with the feed ratio of every gram soil with 1.5～5.0 milligram-atom aluminium or 2.0～5.0 milligram-atom zirconium crosslink agents, under agitation ℃ carry out crosslinking reaction more than 5 minutes in room temperature to 100, use NH during reaction
4The pH value of OH control solution makes it to remain on 4～6;
(4) keep PH4～6, under room temperature to 75 ℃, left standstill aging 0～24 hour;
(5) filtration, washing, drying and roasting.
The purpose of this method is the novel clay molecular sieve with layer structure that a kind of high-temperature hydrothermal stability of preparation is better than existing crosslinked smectite class, not mentioned acid problem about this product in the literary composition.
The object of the present invention is to provide a kind of preparation method with the cross-linked clay that has improved sour amount and strength of acid.
Method provided by the invention is with SO in the preparation process of cross-linked clay
2- 4Appendix is on cross-linked clay, 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 clay slurry of solid content＜5%, particle diameter≤2 micron;
(2) preparation of cross-linking agent solution: it is 0.1～1.0 mole solution that the inorganic metal hydroxy polymer is mixed with concentration of metal ions;
(3) crosslinking reaction: with the feed ratio of every gram soil with 2.0～6.0 mmole metal crosslinking agents, clay slurry is added in the linking agent, under agitation ℃ react more than half an hour in room temperature to 70, the pH value with dilute hydrochloric acid control solution during reaction makes it to remain on below 3;
(4) aging: as to keep PH＜3 after the crosslinking reaction, under room temperature to 70 ℃, left standstill aging 4～24 hours;
(5) filtration, washing, drying: the cross-linking products after the filtration is washed till no Cl with deionized water
-, room temperature to 120 ℃ drying;
(6) appendix SO
2- 4: dried cross-linking products soaked 4～8 hours with 0.1～2.0 mole vitriolic ammonium salt solution, filtered room temperature to 100 ℃ drying;
(7) roasting: 400～650 ℃ of following roastings 1～4 hour.
Said laminated clay both can be natural among the present invention, also can be synthetic; Both can be to have single-storeyed mineral structure, basal spacing (d001) is that the smectite class clay of 0.9～1.5nm (if you would take off soil, wilkinite, Hunk takes off stone, beidellite, vermiculite etc.), also can have regular interbed mineral structure (promptly rearranging) by two kinds of individual layer mineral clay component rule interleaved, the clay of basal spacing (d001) 〉=1.7nm is (as mica-smectite, illite-smectite, glaukonine-smectite, chlorite-smectite, mica-vermiculite, kaolinite-smectite etc.), can also be other clay mixture that contains in the above-mentioned clay one or both.
Said inorganic metal hydroxy polymer is meant the hydroxy polymer of metals such as zirconium, titanium, iron, tin among the present invention, or by more than one are formed among them multipolymer or mixture.They all can adopt various known technologies to be prepared into, for example document (Charles F.Baes, Jr., Robert E.Mesmer, The Hydrolysis of Cations, John Wiley ﹠amp; Sons, New York, 1976, P147～152, P152～158, P226～237, P349～357) described in.
Said vitriolic ammonium salt is meant ammonium sulfate or monoammonium sulfate among the present invention.
The cross-linked clay that adopts method provided by the present invention to prepare has not only kept the original macroporous structure of cross-linked clay, and has stronger acidity, higher acid amount, is 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
With 1 kilogram of natural calcium type rectorite leng (belonging to regular interbed mineral clay), 20 kilograms of deionized waters and exchange capacity are that the strongly acidic styrene of 4 milligramequivalent/grams is that sodium type Zeo-karb mixes for 3 kilograms, 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, recording its solid content is 2.7 heavy %.
With an amount of ZrOCl
28H
2O(Beijing Chemical Plant product, analytical pure) be dissolved in that to make concentration in the deionized water be 0.1 mole the aqueous solution, it is 0.1 mole hydroxyl polymeric zirconium chloride linking agent that aged at room temperature promptly got zirconium concentration in 24 hours.
Feed ratio by the native 3.6 mmole zirconium crosslink agents of every gram is added to clay slurry in the linking agent, and under agitation room temperature reaction is 2 hours, and the pH value with the 0.2NHCl solution hierarchy of control during reaction makes it to remain on below 3.Keep leaving standstill aging 4 hours under PH＜3,70 ℃.Filter, washing is to there not being Cl
-, 120 ℃ of dryings.Dried cross-linking products filters with excessive 0.5 mole ammonium sulfate (Beijing Chemical Plant's product, analytical pure) solution soaking 4 hours, 100 ℃ of dryings, and 500 ℃ of roastings 2 hours were the handy SO that method makes that the invention provides in the air
2- 4/ ZrO
2-rectorite leng layered molecular sieve.
Record its main chemical constitution with the standard chemical method and see Table 1.The scantlings of the structure and the specific surface that records with low-temperature nitrogen adsorption method, the pore volume data that record with conventional x-ray diffraction method see Table 2.
Table 1
Main chemical constitution SiO
2Al
2O
3Fe
2O
3Na
2O
Content, heavy % 45.73 36.17 0.73 2.93
Table 2
Specific surface, pore volume, bed thickness, basal spacing, interlamellar spacing,
Rice
2/ gram milliliter/Ke Nami (d001) nano
181 0.20 1.96 3.50 1.50
Comparative Examples 1
With the rectorite leng is that raw clay, hydroxyl polymeric zirconium chloride are linking agent, according to example 1 described method carry out crosslinking reaction, aging, filter, washing, dry, roasting, prepare not appendix SO
2- 4ZrO
2-rectorite leng layered molecular sieve.
Example 2
Producing wilkinite (belonging to the individual layer mineral clay) with Linan, Zhejiang is that raw clay, hydroxyl polymeric zirconium chloride are linking agent, by the feed ratio of the native 6.0 mmole zirconium crosslink agents of every gram, by example 1 described method carry out crosslinking reaction, aging, filter, washing, dry, appendix SO
2- 4, roasting, prepare with the invention provides the SO that method makes
2- 4/ ZrO
2-bentonite bed column molecular sieve.
Recording its scantlings of the structure with conventional x-ray diffraction method is: bed thickness 0.9 nanometer, basal spacing (d001) 1.96 nanometers, interlamellar spacing 1.06 nanometers.
Comparative Examples 2
With Linan wilkinite is that raw clay, hydroxyl polymeric zirconium chloride are linking agent, by example 2 described methods carry out crosslinking reaction, aging, filter, washing, dry, roasting, prepare not appendix SO
2- 4ZrO
2-bentonite bed column molecular sieve.
Example 3
The invention provides the appendix SO that method makes
2- 4Layered molecular sieve appendix SO more not
2- 4Layered molecular sieve have acid amount and the strength of acid that significantly improves.
Listed example 1,2 in the table 3, the total acid content and the strength of acid of prepared sample in the Comparative Examples 1,2.Total acid content is to adsorb Differential scanning calorimetry (refining of petroleum, 1,6,1979) with ammonia to record, and strength of acid records with the n-butylamine titration method.
Table 3
Sample ZrO
2-rectorite leng ZrO
2-wilkinite
Project is not carried SO
2- 4Carry SO
2- 4Do not carry SO
2- 4Carry SO
2- 4
Total acid content, microvolt 702.5 1567.5 760 1332.5
Total acid content improves, and % 123 75
Strength of acid, Ho+3.3～+ 3.3～+ 3.3～≤-8.2
-3.0 -12.75 -3.0
Example 4
The invention provides the appendix SO that method makes
2- 4Layered molecular sieve appendix SO more not
2- 4Layered molecular sieve have the cracking activity that significantly improves.
With the isopropyl benzene is raw material, and prepared sample in example 1,2 and the Comparative Examples 1,2 is estimated on normal pressure pulse micro-inverse device, and the sample loading amount is 0.1 gram, 300 ℃ of temperature of reaction, and the each sample size of isopropyl benzene is 0.3 microlitre, the results are shown in Table 4.
Table 4
Sample ZrO
2-rectorite leng ZrO
2-rectorite leng
Project is not carried SO
2- 4Carry SO
2- 4Do not carry SO
2- 4Carry SO
2- 4
Transformation efficiency, % 12.0 93.0 37.2 90.8
Transformation efficiency improves % 675 144
Example 5
The invention provides the appendix SO that method makes
2- 4Layered molecular sieve appendix SO more not
2- 4Layered molecular sieve have the alkylation activity that significantly improves.
With the alkylated reaction of prepared sample difference catalysis laurylene and benzene in example 1 and the Comparative Examples 1, the catalyst sample loading amount is 0.1 gram, 83 ℃ of temperature of reaction, and the mol ratio of benzene and laurylene is 5: 1, the results are shown in Table 5.
Table 5
Example reaction time laurylene transformation efficiency
Hour %
ZrO
2-rectorite leng 1 40
SO
2- 4/ ZrO
2-rectorite leng 1 98
SO
2- 4/ ZrO
2-rectorite leng 0.5 92
Example 6
With the rectorite leng is that raw clay, hydroxyl polymeric titanium chloride are the appendix SO that linking agent is prepared
2- 4Layered molecular sieve appendix SO more not
2- 4Layered molecular sieve have the cracking activity that significantly improves.
With TiCl
4(Beijing Chemical Plant's product, analytical pure) is added in 6.0 moles the HCl solution, and thin up is to TiCl
4Concentration be 0.82 mole, aged at room temperature promptly got the hydroxyl polymeric titanium chloride in 7 days, thin up to titanium concentration is 0.1 mole.Rectorite leng clay slurry 185 gram of getting in the example 1 is added in 22 milliliters of hydroxyl polymeric titanium chloride solutions after the dilution, then by the method described in the example 1 carry out crosslinking reaction, aging, filter, washing, dry, appendix SO
2- 4, roasting, prepare with the invention provides the SO that method makes
2- 4/ TiO
2-rectorite leng layered molecular sieve.
Recording its scantlings of the structure with conventional x-ray diffraction method is: bed thickness 1.90 nanometers, basal spacing (d001) 2.60 nanometers, interlamellar spacing 0.70 nanometer.
Carry out the evaluation of isopropyl benzene cracking activity, SO according to example 4 described conditions
2- 4/ TiO
2The transformation efficiency of-rectorite leng sample is 82.0%, and appendix SO not
2- 4TiO
2The transformation efficiency of-rectorite leng sample only is 14.5%.
Example 7
With the rectorite leng is that raw clay, hydroxyl polymeric zirconium chloride-titanium are the appendix SO that linking agent is prepared
2- 4Layered molecular sieve appendix SO more not
2- 4Layered molecular sieve have the cracking activity that significantly improves.
With an amount of ZrOCl
28H
2O is dissolved in that to make concentration in the deionized water be 1.0 moles the aqueous solution.With 0.82 mole TiCl in the example 6
4Solution according to the Ti/Zr mol ratio be 1: 1 consumption therewith zirconium solution mix, one week of aged at room temperature promptly gets hydroxyl polymeric zirconium chloride-titanium mixed cross-linker, thin up to zirconium concentration is 0.1 mole.According to the method described in the example 1 carry out crosslinking reaction, aging, filter, washing, dry, appendix SO
2- 4: roasting, prepare with the invention provides the SO that method makes
2- 4/ TiO
2-ZrO
2-rectorite leng layered molecular sieve.
Recording its scantlings of the structure with conventional x-ray diffraction method is: bed thickness 1.90 nanometers, basal spacing (d001) 3.20 nanometers, interlamellar spacing 1.30 nanometers.
Carry out the evaluation of isopropyl benzene cracking activity, SO according to example 4 described conditions
2- 4/ TiO
2-ZrO
2The transformation efficiency of-rectorite leng sample is 80.0%, and appendix SO not
2- 4TiO
2-ZrO
2The transformation efficiency of-rectorite leng sample only is 14.5%.
Claims (6)
1, a kind of preparation method of cross-linked clay, comprise with make after calcium type laminated clay transition slurries, with inorganic metal hydroxy polymer solution be mixed with finite concentration, make that said two devices carries out that crosslinking reaction, control pH value are aging, filtration washing, drying, roasting, it 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 techniques, makes the clay slurry of solid content＜5%, particle diameter≤2 micron;
(2) the inorganic metal hydroxy polymer being mixed with concentration of metal ions is 0.1～1.0 mole solution;
(3) with the feed ratio of every gram soil with 2.0～6.0 mmole metal crosslinking agents, clay slurry is added in the linking agent, under agitation more than room temperature to 70 ℃ reaction half an hour, the pH value of controlling solution with dilute hydrochloric acid during reaction makes it to remain on below 3;
(4) keep PH＜3, under room temperature to 70 ℃, left standstill aging 4～24 hours;
(5) filtration, washing, drying;
(6) soaked cross-linking products 4～8 hours with 0.1～2.0 mole vitriolic ammonium salt solution, filter, drying;
(7) 400～650 ℃ of following roastings 1～4 hour.
2, according to the described preparation method of claim 1, it is characterized in that said laminated clay be meant natural or synthetic have single-storeyed mineral structure, basal spacing (d001) is the smectite class clay of 0.9～1.5nm, or have the clay of regular interbed mineral structure, basal spacing (d001) 〉=1.7nm, or contain in the above-mentioned clay one or both other clay mixture.
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, illite-smectite, glaukonine-smectite, chlorite-smectite, mica-vermiculite, kaolinite-smectite etc. according to the described preparation method of claim 2.
5,, it is characterized in that said inorganic metal hydroxy polymer is meant the hydroxy polymer of metals such as zirconium, titanium, iron, tin 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 vitriolic ammonium salt is meant ammonium sulfate or monoammonium sulfate according to the described preparation method of claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88108611 CN1018817B (en) | 1988-12-17 | 1988-12-17 | Process for preparing cross-linking clay with increased acidic property |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 88108611 CN1018817B (en) | 1988-12-17 | 1988-12-17 | Process for preparing cross-linking clay with increased acidic property |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1043270A CN1043270A (en) | 1990-06-27 |
| CN1018817B true CN1018817B (en) | 1992-10-28 |
Family
ID=4835134
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 88108611 Expired CN1018817B (en) | 1988-12-17 | 1988-12-17 | Process for preparing cross-linking clay with increased acidic property |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1018817B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056869C (en) * | 1996-03-21 | 2000-09-27 | 中国石油化工总公司 | Olefinpoducing-modified layered clay catalyst and its production and use |
| CN1060204C (en) * | 1997-09-17 | 2001-01-03 | 中国石油化工总公司 | Laminar column clay microphere cracking catalyst for heavy oil and its preparation |
| JP4404991B2 (en) * | 1999-06-01 | 2010-01-27 | 水澤化学工業株式会社 | Active white clay shaped particles, production method thereof and use thereof |
| CN102294244A (en) * | 2011-06-17 | 2011-12-28 | 金玲 | Method for improving surface catalytic activities of catalyst particles |
| WO2018081448A1 (en) | 2016-10-26 | 2018-05-03 | The Board Of Trustees Of The Leland Stanford Junior University | Modified immunoglobulin hinge regions to reduce hemagglutination |
| CN108622908A (en) * | 2018-05-21 | 2018-10-09 | 东北大学 | A kind of method that clay alteration prepares pale yellow-reddish brown colour system mineral material |
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1988
- 1988-12-17 CN CN 88108611 patent/CN1018817B/en not_active Expired
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|---|---|
| CN1043270A (en) | 1990-06-27 |
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