CN1095689C - Process for preparing aluminium oxide-titanium oxide bicomponent - Google Patents

Process for preparing aluminium oxide-titanium oxide bicomponent Download PDF

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CN1095689C
CN1095689C CN99112941A CN99112941A CN1095689C CN 1095689 C CN1095689 C CN 1095689C CN 99112941 A CN99112941 A CN 99112941A CN 99112941 A CN99112941 A CN 99112941A CN 1095689 C CN1095689 C CN 1095689C
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titanium
sample
component
roasting
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CN1273878A (en
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蒋宗轩
李国强
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Sinopec Fushun Research Institute of Petroleum and Petrochemicals
China Petrochemical Corp
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Sinopec Fushun Research Institute of Petroleum and Petrochemicals
China Petrochemical Corp
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Abstract

The present invention relates to a method for preparing cheap titanium oxide and alumina (Ti-Al) bicomponents having high dispersivity and used as catalysts and catalyst carriers. The titanium oxide and alumina bicomponents are prepared from soluble titanium salts, the mixed solution of soluble aluminum salts, and NaAlO2 solution in a cocurrent flow mode with a coprecipitation method, and are preferably prepared from (TiCl4+AlCl3), solution [TiCl4+Al2(SO4)3] and solution NaAlO2 in a cocurrent flow mode with a coprecipitation method. The Ti-Al bicomponents are prepared from 0.5 wt% to 50 wt% of titanium oxide. The Ti-Al bicomponents have the advantages of simple preparation method, easy acquirement of raw materials, large specific surface area, high dispersivity, etc.

Description

A kind of preparation method of aluminium oxide-titanium oxide bicomponent
Technical field
The present invention relates to the preparation of a kind of titanium dioxide-aluminum oxide (Ti-Al) bi-component, more particularly, relate to the preparation of cheap high dispersive titanium dioxide-aluminum oxide (Ti-Al) bi-component of a kind of useful as catalysts and catalyst base.
Background technology
Ti-Al bi-component and preparation method thereof has many reports.The Ti-Al bi-component is commonly used for the carrier in the petrochemical industry hydrorefining catalyst for hydrocarbon on the one hand; The Ti-Al bi-component also can be directly used among gram Lloyd's (Claus) catalyst process on the other hand.
Traditional Ti-Al bi-component adopts alumina dry glue to add an amount of peptizing agent again with the mixture of titanium oxide and water fully mixes after moulding, drying, roasting make.As European patent prospectus (publication number 0,199,399) disclose the method for making of making catalyst base with the Ti-Al bi-component in, the method for making of this Ti-Al bi-component is a certain proportion of aluminium oxide, titanium oxide, acetate and water to be added to mix pinching molded together, and high-temperature roasting makes again.The characteristics of this Ti-Al bi-component are catalyst initial activity height, but titanium oxide decentralization, mechanical strength and life-span are unsatisfactory.Also having some is to utilize γ-Al 2O 3Be skeleton, the acid solution of dipping titanium salt is [as TiCl 4, Ti (SO 4) 2Deng], with becoming titanium oxide after hydrolysis adds the thermal decomposition titanium salt.Although this method is being of great benefit to aspect the specific area that improves carrier, but the Ti-Al bi-component for preparing high-load titanium (greater than 5wt%) acquires a certain degree of difficulty, its reason is that most of titanium oxide changes into the titanium oxide that the crystalline phase inactive, that decentralization is relatively poor is a rutile, thus catalyst will to keep its highly active life-span shorter.Other example is to make the Ti-Al bi-component with water-soluble titanium salt and sodium aluminate solution co-precipitation.Prepare the Ti-Al bi-component as disclosing in the European patent prospectus (publication number 0,339,640) with titanium trichloride or titanyl sulfate or dichloro oxygen titanium and sodium aluminate solution coprecipitation.With this Ti-Al bi-component CS that is catalyst 2The Claus conversion process have advantages such as active height, stable height and anti-sulphur are strong.But the place that this catalyst also haves much room for improvement.
1, its titanium source price is higher, and it does not adopt the high titanium tetrachloride of relative low price purity as the titanium source, and its reason is that titanium tetrachloride and water reaction are too violent, is difficult to control its reaction speed.2, adopt the reaction of titanium salt and sodium aluminate solution to adopt titanium aluminium mixed solution and sodium aluminate solution reaction, the amount of the titanium aluminium carrier that generates in unit interval, unit volume is less, and the industrial production cost is higher.3, the specific area of Ti-Al component also needs further raising.
Summary of the invention
Purpose of the present invention is just in order to solve above-mentioned three aspect problems.The preparation method of the Ti-Al component that a kind of preparation method is simple, raw material is easy to get, specific area is big is provided.
Utilize the high titanium tetrachloride of relative low price purity as the titanium source among the present invention, mix with the aluminum soluble salt crystal, titanium tetrachloride is adsorbed onto on the aluminum soluble salt crystal, can avoids the reaction of titanium tetrachloride and water too violent like this, thereby reach the purpose of control reaction speed.On the other hand, utilize titanium aluminum solutions and sodium aluminate solution co-precipitation, can improve the amount of the Ti-Al bi-component that generates in unit interval, the unit volume greatly, thereby reduce production costs greatly.At last, adopt the specific area of Ti-Al bi-component of the identical titanium oxide content of this method preparation to be greatly improved.
According to the Ti-Al bi-component that this method is produced, its production cost cost by the production of method described in the above-mentioned European patent prospectus (publication number 0,339,640) Ti-Al bi-component is low more than 30%.The specific area of the Ti-Al bi-component of identical titanium oxide content can improve more than 20%.
The preparation method of Ti-Al bi-component of the present invention is as follows:
1, the preparation of titanium aluminum solutions: with solubility titanium salt and water-soluble aluminium salt crystal by weight 5 * 10 -3～0.7, wherein water-soluble aluminium salt crystal is aluminium chloride, aluminum sulfate or aluminum nitrate etc. preferably, and the solubility titanium salt is preferably TiCl 4, progressively drip deionized water then, dissolving under agitation, the elimination insoluble matter obtains the titanium aluminum solutions.
2, the preparation of sodium aluminate solution: the sodium metaaluminate solid is soluble in water, stirring and dissolving, the elimination insoluble matter obtains the sodium aluminate solution that concentration is 1wt%～20wt%.
3, under agitation, above-mentioned titanium aluminum solutions and sodium aluminate solution are 20 ℃～70 ℃ and flow co-precipitation in reaction temperature, under this reaction temperature, reacted 1～3 hour, regulate pH value to 8.5～10 with ammoniacal liquor, placement is spent the night, suction filtration, washing, making beating back obtains the dry sample of Ti-Al 80 ℃～150 ℃ spray-dryings 2～8 hours.The specific area that records the dry sample of this Ti-Al with nitrogen absorption (BET) method is 200～450m 2/ g, recording total pore volume with nitrogen adsorption method is 0.1～1.5ml/g, average pore size is 2～13nm.
4, be W by weight percentage HNO3/ W The dry sample of Ti-Al=0.010～0.025, W H2O/ W The dry sample of Ti-Al=0.50～1.0 ratio is extruded into various suitable shapes after pinching with dry sample of Ti-Al and aqueous solution of nitric acid are fully mixed, as cloverleaf pattern, bar shaped, sphere etc.; Dry in the shade in room temperature, 100～150 ℃ of oven dry 2～8 hours, progressively be warming up to 450～650 ℃, roasting 2～8 hours makes the Ti-Al bi-component that contains titanium oxide 0.5wt%～50wt%.The specific area that records this bi-component with nitrogen absorption (BET) method is 200～400m 2/ g, recording total pore volume with nitrogen adsorption method is 0.1～1.5ml/g, average pore size is 2～15nm.
The purposes of Ti-Al bi-component of the present invention is to be used as catalyst base in hydrocarbons hydrogenation is refining, is specially adapted to hydrodenitrogeneration (HDN) and hydrodesulfurization (HDS) process are risen simultaneously the catalyst base of catalytic action; Catalyst of the present invention also can be used for substituting traditional Ti-Al gram Lloyd's (Claus) catalyst, and (organic sulfur compound is converted into H 2The catalyst of S and S).
The specific embodiment
In order to further specify the present invention, enumerate following examples and contrast experiment, but it does not limit the defined invention scope of each accessory claim.
Example I
1, the preparation of titanium aluminum solutions: with the TiCl of 1ml (density is 1.726g/ml) 4Join the AlCl of 360 grams 36H 2In the O crystalline solid, progressively drip deionized water then, dissolving under agitation, last thin up is to 1000ml, and the elimination insoluble matter obtains the titanium aluminum solutions.The hydrogen chloride gas that produces in the course of dissolution is introduced in the hydrogen chloride gas recovery pond.
2, the preparation of sodium aluminate solution: 500ml water is joined in the sodium metaaluminate solid of 110 grams, stirring and dissolving, last thin up is to 1000ml, and the elimination insoluble matter obtains sodium aluminate solution.
3, under agitation, with above-mentioned titanium aluminum solutions and sodium aluminate solution with 55 ℃ of flow velocity, the reaction temperatures of 17ml/min. and flow co-precipitation, reaction is 2 hours under this reaction temperature, last mother liquor pH value is 6, regulate pH value to 9.5 with ammoniacal liquor, placement is spent the night, suction filtration, washing, making beating back obtains the dry sample of Ti-Al 120 ℃ of spray-dryings 3 hours.
4, restrain the dry sample of above-mentioned Ti-Al and contain HNO 133 32.5 the 100ml aqueous solution of gram fully mixes and pinches, and is extruded into cloverleaf pattern with banded extruder; Dry in the shade in room temperature,, progressively be warming up to 480 ℃ 120 ℃ of oven dry 4 hours, and should the drying sample 480 ℃ of following roastings 7 hours, make the Ti-Al roasting sample that is loaded with titanium oxide 0.5wt%.The specific area that records this roasting sample with nitrogen absorption (BET) method is 340m 2/ g, recording total pore volume with nitrogen adsorption method is 0.490ml/g, average pore size is 5.76nm.This roasting sample is represented with Ti-Al-1.
Example II
1, the preparation of titanium aluminum solutions: same example I, wherein TiCl 4Addition be 11ml.
2, the preparation of sodium aluminate solution: same example I.
3, same example I makes the dry sample of Ti-Al.
4, same example I, wherein should the drying sample under 550 ℃, roasting 5 hours makes the Ti-Al roasting sample that is loaded with titanium oxide 5wt%.The specific area that records this roasting sample with nitrogen absorption (BET) method is 345m 2/ g, recording total pore volume with nitrogen adsorption method is 0.504ml/g, average pore size is 5.84nm.This roasting sample is represented with Ti-Al-2.
EXAMPLE III
1, the preparation of titanium aluminum solutions: same example I, just TiCl 4Addition be 22.5ml.
2, the preparation of sodium aluminate solution: same example I.
3, same example I makes the dry sample of Ti-Al.
4, same example I, wherein should the drying sample under 500 ℃, roasting 4 hours makes the Ti-Al roasting sample that is loaded with titanium oxide 10wt%.The specific area that records this roasting sample with nitrogen absorption (BET) method is 355m 2/ g, recording total pore volume with nitrogen adsorption method is 0.535ml/g, average pore size is 6.03nm.This roasting sample is represented with Ti-Al-3.
EXAMPLE IV
1, the preparation of titanium aluminum solutions: same example I, wherein TiCl 4Addition be 35.5ml.
2, the preparation of sodium aluminate solution: same example I.
3, same example I makes the dry sample of Ti-Al.
4, same example I, wherein should the drying sample under 550 ℃, roasting 6 hours makes the Ti-Al roasting sample that is loaded with titanium oxide 15wt%.The specific area that records this roasting sample with nitrogen absorption (BET) method is 330m 2/ g, recording total pore volume with nitrogen adsorption method is 0.540ml/g, average pore size is 6.54nm.This roasting sample is represented with Ti-Al-4.
EXAMPLE V
1, the preparation of titanium aluminum solutions: same example I, wherein TiCl 4Addition is 50ml.
2, the preparation of sodium aluminate solution: same example I.
3, same example I makes the dry sample of Ti-Al.
4, same example I, wherein should the drying sample under 600 ℃, roasting 2.5 hours makes the Ti-Al roasting sample that is loaded with titanium oxide 20wt%.The specific area that records this roasting sample with nitrogen absorption (BET) method is 320m 2/ g, recording total pore volume with nitrogen adsorption method is 0.520ml/g, average pore size is 6.50nm.This roasting sample is represented with Ti-Al-5.
Example VI
1, the preparation of titanium aluminum solutions: same example I, wherein TiCl 4Addition is 66.5ml.
2, the preparation of sodium aluminate solution: same example I.
3, same example I makes the dry sample of Ti-Al.
4, same example I, wherein should the drying sample under 500 ℃, roasting 4 hours makes the Ti-Al roasting sample that is loaded with titanium oxide 25wt%.The specific area that records this roasting sample with nitrogen absorption (BET) method is 315m 2/ g, recording total pore volume with nitrogen adsorption method is 0.500ml/g, average pore size is 6.35nm.This roasting sample is represented with Ti-Al-6.
Example VII A
1, the preparation of titanium aluminum solutions: same example I, wherein TiCl 4Addition is 85.5ml.
2, the preparation of sodium aluminate solution: same example I.
3, same example I makes the dry sample of Ti-Al.
4, same example I, wherein should the drying sample at 500 ℃, roasting 4 hours makes the Ti-Al roasting sample that is loaded with titanium oxide 30wt%.The specific area that records this roasting sample with nitrogen absorption (BET) method is 300m 2/ g, recording total pore volume with nitrogen adsorption method is 0.485ml/g, average pore size is 6.47nm.This roasting sample is represented with Ti-Al-7.
Example VII A I
1, the preparation of titanium aluminum solutions: same example I, wherein TiCl 4Addition is 107.5ml.
2, the preparation of sodium aluminate solution: same example I.
3, same example I makes the dry sample of Ti-Al.
4, same example I, wherein should the drying sample at 490 ℃, roasting 4 hours makes the Ti-Al roasting sample that is loaded with titanium oxide 35wt%.The specific area that records this roasting sample with nitrogen absorption (BET) method is 285m 2/ g, recording total pore volume with nitrogen adsorption method is 0.475ml/g, average pore size is 6.67nm.This roasting sample is represented with Ti-Al-8.
Example I X
1, the preparation of titanium aluminum solutions: same example I, wherein TiCl 4Addition is 133ml.
2, the preparation of sodium aluminate solution: same example I.
3, same example I makes the dry sample of Ti-Al.
4, same example I, wherein should the drying sample at 460 ℃, roasting 4 hours makes the Ti-Al roasting sample that is loaded with titanium oxide 40wt%.The specific area that records this roasting sample with nitrogen absorption (BET) method is 270m 2/ g, recording total pore volume with nitrogen adsorption method is 0.470ml/g, average pore size is 6.96nm.This roasting sample is represented with Ti-Al-9.
Comparative Examples I
Pressing in the European patent prospectus (publication number 0,339,640) disclosed method, to prepare the Ti-Al bi-component as follows: with 243 gram NaAlO 2Be dissolved in the 1000ml water, the elimination insoluble matter makes NaAlO 2Solution.To contain TiOCl 2The aqueous solution of 41 grams is diluted to 1000ml, makes TiOCl 2The aqueous solution.Above-mentioned two kinds of solution are reacted in the speed adding reactor with 125ml/min. simultaneously.Reaction temperature is controlled at 55 ℃, and in 2 hours reaction time, reacting last mother liquor pH value is 6, regulates pH value to 9.5 with ammoniacal liquor, and placement is spent the night, suction filtration, washing, and the making beating back obtains Ti-Al drying sample 110 ℃ of spray-dryings 4 hours.Restrain the dry sample of above-mentioned Ti-Al and contain HNO 133 32.5 the 100ml aqueous solution of gram fully mixes and pinches, and is extruded into cloverleaf pattern with banded extruder; Dry in the shade in room temperature, 120 ℃ of oven dry 4 hours, progressively be warming up to 550 ℃, roasting 5 hours makes the Ti-Al roasting sample that is loaded with titanium oxide 15wt%.The specific area that records this roasting sample with nitrogen absorption (BET) method is 260m 2/ g, recording total pore volume with nitrogen adsorption method is 0.520ml/g, average pore size is 8.00nm.This roasting sample is represented with Ti-Al-10.The pore structure of the dry sample of Ti-Al is as shown in table 1.
The pore structure of the dry sample of table 1 Ti-Al
Sample number into spectrum TiO 2Content (wt%) Nitrogen absorption (BET) surface area (m 2/g) Pore volume (ml/g) Average pore size (nm) XRD result
Ti-Al-1 0.5 420 0.530 5.05 α-one water aluminium oxide
Ti-Al-2 5 425 0.563 5.30 α-one water aluminium oxide
Ti-Al-3 10 433 0.591 5.46 α-one water aluminium oxide
Ti-Al-4 15 410 0.584 5.70 α-one water aluminium oxide
Ti-Al-5 20 380 0.560 5.90 α-one water aluminium oxide
Ti-Al-6 25 360 0.554 6.15 α-one water aluminium oxide
Ti-Al-7 30 335 0.533 6.37 α-one water aluminium oxide
Ti-Al-8 35 300 0.485 6.47 α-one water aluminium oxide
Ti-Al-9 40 290 0.483 6.66 α-one water aluminium oxide
Ti-Al-10 15 300 0.650 8.67 α-one water aluminium oxide
The pore structure of Ti-Al roasting sample is as shown in table 2.
The pore structure of table 2 Ti-Al roasting sample
Sample number into spectrum TiO 2Content (wt%) Nitrogen absorption BET surface area (m 2/g) Pore volume (ml/g) Average pore size (nm) XRD result
Ti-Al-1 0.5 340 0.490 5.76 γ-Al 2O 3
Ti-Al-2 5 345 0.504 5.84 γ-Al 2O 3
Ti-Al-3 10 355 0.535 6.03 γ-Al 2O 3
Ti-Al-4 15 330 0.540 6.54 γ-Al 2O 3
Ti-Al-5 20 320 0.520 6.50 γ-Al 2O 3+TiO 2(A)
Ti-Al-6 25 315 0.500 6.35 γ-Al 2O 3+TiO 2(A)
Ti-Al-7 30 300 0.485 6.47 γ-Al 2O 3+TiO 2(A)
Ti-Al-8 35 285 0.475 6.67 γ-Al 2O 3+TiO 2(A)
Ti-Al-9 40 270 0.470 6.96 γ-Al 2O 3+TiO 2(A)
Ti-Al-10 15 260 0.520 8.00 γ-Al 2O 3+TiO 2(A)
Above-mentioned table 1, table 2 result show, with the identical TiO that has of this method preparation 2The specific area of dry sample of the Ti-Al of content and roasting sample (sample number into spectrum is Ti-Al-4) is all than the height of contrast experiment's (sample number into spectrum is Ti-Al-10); The XRD presentation of results is with the identical TiO that has of this method preparation 2The TiO of the Ti-Al roasting sample of content 2Decentralization is than contrast experiment's height.

Claims (6)

1, the preparation method of the titanium dioxide-aluminum oxide of a kind of useful as catalysts and catalyst base (Ti-Al) bi-component:
(1) preparation of titanium aluminum solutions: with solubility titanium salt and water-soluble aluminium salt crystal by weight 5 * 10 -3～0.7 mixes, and progressively drips deionized water then, dissolving under agitation, and the elimination insoluble matter obtains the titanium aluminum solutions;
(2) preparation of sodium aluminate solution: the sodium metaaluminate solid is soluble in water, stirring and dissolving, the elimination insoluble matter obtains the sodium aluminate solution that concentration is 1wt%～20wt%;
(3) under agitation, above-mentioned titanium aluminum solutions and sodium aluminate solution are 20 ℃～70 ℃ and flow co-precipitation in reaction temperature, under this reaction temperature, reacted 1～3 hour, regulate pH value to 8.5～10 with ammoniacal liquor, placement is spent the night, suction filtration, washing, making beating back obtains the dry sample of Ti-Al 80 ℃～150 ℃ spray-dryings 2～8 hours;
(4) W by weight percentage HNO3/ W The dry sample of Ti-Al=0.010～0.025, W H2O/ W The dry sample of Ti-Al=0.50～1.0 ratio is fully mixed dry sample of Ti-Al and aqueous solution of nitric acid and is extruded into various suitable shapes after pinching, and dries in the shade in room temperature, dries 2～8 hours at 100～150 ℃, progressively is warming up to 450～650 ℃, and roasting 2～8 hours makes the Ti-Al bi-component.
2, according to the described preparation method of claim 1, wherein the water-soluble aluminium salt crystal described in the step (1) is aluminium chloride, aluminum sulfate, aluminum nitrate or its composition.
3, according to the described preparation method of claim 1, wherein the solubility titanium salt described in the step (1) is TiCl 4
4, according to the described preparation method of claim 1, the dry sample of the Ti-Al described in the step (3) wherein, recording its specific area with nitrogen adsorption method is 200～450m 2/ g, total pore volume is 0.1～1.5ml/g, average pore size is 2～13nm.
5, the prepared Ti-Al bi-component of a kind of preparation method according to claim 1, wherein recording its specific area with nitrogen adsorption method is 200～400m 2/ g, total pore volume is 0.1～1.5ml/g, average pore size is 2～15nm.
6, according to the described Ti-Al bi-component of claim 5, wherein contain TiO 2Be 0.5wt%～50wt%, all the other are Al 2O 3
CN99112941A 1999-05-18 1999-05-18 Process for preparing aluminium oxide-titanium oxide bicomponent Expired - Fee Related CN1095689C (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100363298C (en) * 2006-04-11 2008-01-23 浙江大学 Process for preparing aluminum titanium composite oxide with high specific surface
CN100441298C (en) * 2004-04-20 2008-12-10 中国石油化工股份有限公司 Titanium oxide - aluminum oxide composite carrier, preparation method and application thereof

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN113086999A (en) * 2021-04-15 2021-07-09 天津凯文特科技有限公司 Novel preparation method of titanium modified activated alumina dry glue

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Publication number Priority date Publication date Assignee Title
US4061689A (en) * 1975-12-29 1977-12-06 Uop Inc. Process for the conversion of aromatic hydrocarbons
EP0218153A2 (en) * 1985-09-28 1987-04-15 BASF Aktiengesellschaft Process for eliminating sulfur compounds from gas streams

Patent Citations (2)

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US4061689A (en) * 1975-12-29 1977-12-06 Uop Inc. Process for the conversion of aromatic hydrocarbons
EP0218153A2 (en) * 1985-09-28 1987-04-15 BASF Aktiengesellschaft Process for eliminating sulfur compounds from gas streams

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100441298C (en) * 2004-04-20 2008-12-10 中国石油化工股份有限公司 Titanium oxide - aluminum oxide composite carrier, preparation method and application thereof
CN100363298C (en) * 2006-04-11 2008-01-23 浙江大学 Process for preparing aluminum titanium composite oxide with high specific surface

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