CN1351115A - Demetalating and desulfurizing hydrocatalyst and its preparing process - Google Patents
Demetalating and desulfurizing hydrocatalyst and its preparing process Download PDFInfo
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Abstract
A hydrocatalyst for demetalating and desulfurizing heavy oil is prepared through mixing two kinds of alumina with different natures with the solution contain metals in families VIB and VIII, extruding out bar, shaping, drying and calcining and features that in its preparing process, less B and at least one of alkali metal and alkali-earth metal are added.
Description
The present invention relates to a kind of preparation of hydrotreating catalyst, especially for the Catalysts and its preparation method of heavy oil hydrogenation demetal and hydrogenating desulfurization.
Sulfur in heavy oil, heavy metal (as V, Ni) wait foreign matter content higher, and molecular volume are bigger, so require catalyzer to have macroporous structure.In the mink cell focus hydrogenation process, catalyzer is contaminated serious, is difficult to regeneration in addition, so, require to reduce the Preparation of Catalyst cost.As select low-cost raw material and simplify preparation technology etc.
At present, it is carrier that this type of catalyzer usually adopts porous oxide compound such as aluminum oxide, is active constituent with group vib metal such as W or Mo and VIII family metal Co or Ni.Method for preparing catalyst mainly contains: coprecipitation method, kneading method and pickling process etc.
US4 adopts in 671,866 coprecipitation method to prepare catalyzer, this catalyst surface area 112m
2/ g, pore volume 1.03ml/g, mean pore size 37.6nm.Though this catalyzer has larger aperture and pore volume, specific surface area is lower.And, this method complicated operation, production cost height.
By contrast, kneading method is operated fairly simple convenience, implements easily, helps reducing the catalyzer manufacturing cost.Adopt kneading method to prepare catalyzer, maturing temperature can not be too high, otherwise reactive metal and carrier generation strong interaction reduce catalyst activity.But maturing temperature is too low, then is difficult to obtain the required macropore of heavy-oil hydrogenation (especially demetalization) catalyzer.
For addressing this problem, US4,411,824 when preparing catalyzer with kneading method, adopted steam-treated, and the catalyzer aperture is increased.This inventive method has certain reaming effect when hanging down for active metal component, is 0.92w% as working as active ingredient CoO, MoO
3During for 2.8w%, catalyst surface area is 184m
2/ g, pore volume 1.01ml/g, mean pore size 18nm; But being increased to CoO when active ingredient is 3.1w%, MoO
3During for 9.2w%, the catalyzer mean pore size is little, is 11.5nm, uncomfortable cooperation catalyst for heavy oil hydrogenation demetal.
Some patent is improved the catalyzer physico-chemical property by adding auxiliary agent, to remedy owing to the low problem that causes the catalyst hydrogenation activity difference of specific surface area.As US6, in 037, the 300 described catalyst preparation process, adding auxiliary agent boron, silicon and/or phosphorus, fluorine improve the surface acidity of catalyzer.The mode that this catalyzer adds auxiliary agent is, with the carrier of the solution impregnation moulding that contains auxiliary agent.Contain group vib 3-60w% (by oxide compound, down together) on this catalyzer, contain the metal 0.1-30w% of VIII family, boracic 0.1-20w%.This catalyzer is applicable to fraction oil hydrodesulfurizing and hydrocracking process.Handle for heavy-oil hydrogenation, this acidity of catalyst is too strong, and the green coke reaction is accelerated, and coke deposits rapidly on catalyst surface, causes catalyst deactivation.
At the problem that exists in the present technology, the invention provides the heavy oil hydrogenation demetal and the Hydrobon catalyst of a kind of hydrogenation activity height, good stability, another object of the present invention provides that a kind of process is easy, cost is low, the preparation method of the heavy oil hydrogenation demetal of flexible operation and Hydrobon catalyst.
Catalyzer of the present invention contains group vib metal 2-14w% (by oxide compound, down together), preferably 5-10w% by weight; Contain the metal 0.1-8w% of VIII family, 2-4w% preferably, containing boron oxide is 0.1-5w%, preferably 0.5-2w%; Contain I A family or IIA family metal is 0.1-5w%, preferably 0.5-2w%; Remainder is an aluminum oxide.The pore volume of catalyzer is 0.5-1.3ml/g, is preferably 0.7-1.0ml/g, and specific surface area is 120-240m
2/ g, preferably 130-190m
2/ g, mean pore size is 8.5-43nm, preferably 15-30nm.This catalyzer aperture accounts for more than 70% of total pore volume at the pore volume between the 5-30nm, and the pore volume of aperture 〉=16nm accounts for 50% of total pore volume at least.
Method for preparing catalyst of the present invention is: get a certain amount of aluminum oxide, with the metal-salt that contains requirement concentration (being selected from group vib metal and VIII family metal) solution, contain IA family or IIA family metallic solution and boron-containing solution etc., press catalyzer and form the mixed pinching bar moulding of ratio requirement, dry then, roasting, the preparation catalyzer.
The concrete preparation process of catalyzer of the present invention is:
(1) gets certain amount of alumina, as aluminium hydroxide (being pseudo-boehmite) and/or γ-Al
2O
3(2) boric acid is dissolved in the ammoniacal liquor at a certain temperature, gets solution A; (3) the water heating for dissolving contains the compound of IA or IIA metal, gets solution B; (4) salt that will contain group vib and VIII family metal is dissolved in ammonia and the aqueous citric acid solution, obtains the active metal component solution C; (5) peptizing agent is dissolved in the suitable quantity of water, gets solution D.
With material in (1) and solution A, B, C and D mixed pinch become plastic after, extruded moulding.Extruded material descended dry 2-8 hour at 80-200 ℃, or placed a night, then at 500-800 ℃ of following roasting 0.5-5 hour, obtained catalyzer of the present invention.
Above-mentioned (1) can be a kind of aluminum oxide, adjust pore distribution and preferably use two kinds of aluminum oxide of different nature for convenient, as a kind of be to amass higher aluminum oxide than table, another kind is the more aluminum oxide of macropore content.Two kinds of different aluminum oxide are (as pseudo-boehmite and γ-Al
2O
3, two kinds of thin water aluminium of different plans, two kinds of different γ-Al
2O
3) ratio is 1: 25-25: 1 (weight).
Above-mentioned (3) IA family metal is preferably potassium or sodium, and its compound is nitrate, carbonate, muriate, oxyhydroxide etc.IIA family metal is preferably magnesium or calcium, and its compound is muriate, oxyhydroxide, carbonate etc.
Group vib metal described in above-mentioned (4) is W or Mo, and selected salt is preferably ammonium salt; VIII family metal is Co or Ni, and selected salt is nitrate, carbonate, acetate or muriate etc., is preferably carbonate or acetate.
Peptizing agent described in above-mentioned (5) is formic acid, acetate or nitric acid, hydrochloric acid etc., and peptizing agent content is 0.3-4.0w% (is benchmark with alumina content in the material).
In kneading process, also can add an amount of extrusion aid such as polyvinyl alcohol, methylcellulose gum, sesbania powder and carbon black etc.These materials can play lubricated when extrusion and help the effect of squeezing, and in roasting process, owing to be oxidized to volatilizable material, have certain reaming effect simultaneously.Extrusion aid content is 1.5-5.5w% (being as the criterion with alumina content in the material).
Catalyzer of the present invention, aperture and pore volume are bigger, and specific surface area is moderate, and catalyst activity change of component a wider range has good hydrogenation activity and stability, goes for polytype heavy, residuum hydrogenating and metal-eliminating and hydrodesulfurization process.
Compared with prior art, the present invention has simplified preparation process, and is easy to operate, helps reducing the Catalyst Production cost.Use two kinds of aluminum oxide of different nature, the grain fineness number difference in mixing process, changes the stacking states of original aluminum oxide, can adjust the pore structure of catalyzer neatly.The metal salt solution preparation method is simple, and solution is alkalescence, helps reducing the acidity of catalyzer.In the drying and roasting process, the decomposition of all cpds also can be played certain reaming effect in the solution.The present invention adds pore structure and the surface chemical property that a spot of boron can improve catalyzer, helps improving the hydrogenation activity and the stability of catalyzer.IA family or IIA family element belong to basic metal, can reduce the acidity of catalyzer, and simultaneously, IA family or IIA family metal also can suppress reactive metal and alumina catalyst support generation strong interaction, improve catalyst hydrogenation activity.
Further describe the present invention below in conjunction with embodiment.
Embodiment 1
(1) takes by weighing 500g by aluminum hydroxide solid elastomer powder (water content 30%) and 500g V250 powder and 21g carbon black that first fertilizer plant of Chinese Qilu Petrochemical company produces, mix.
(2) get that 4g boric acid adds 110ml, concentration is in the ammoniacal liquor of 12w%, heated and stirred is dissolved boric acid fully, solution a1.
(3) the 2.9g magnesium chloride joins in the 50g water, and heated and stirred makes it abundant dissolving, gets solution b1.
(4) get the 102g ammonium molybdate, the 48g nickelous carbonate, the 68g citric acid, adding 540ml concentration is the ammoniacal liquor of 14w%, stirring and dissolving.Be that 58% ammoniacal liquor and water purification transfer to 10 with the pH value of solution value with concentration then, liquor capacity is 600ml, solution c1.
(3) be that the acetate of 99w% is dissolved in the 200g water with 17g concentration, solution d1.
(4) solid materials in (1) is mixed with solution a1, b1, c1 and d1, become (mixture pH value is 6.5) behind the plastic extruded moulding on banded extruder.
(5) with the extruded moulding material under 100 ℃, dry 8 hours.
(6) with material after the drying under 600 ℃, roasting 3 hours obtains catalyzer C1.
Embodiment 2
(1) take by weighing with embodiment 1 in identical aluminum hydroxide solid elastomer powder 500g and baked aluminum oxide powder 50g and 12g sesbania powder, mix.
(2) 4.6g boric acid joins 90ml, concentration is in the ammoniacal liquor of 12w%, and heated and stirred is dissolved boric acid fully, gets solution a2.
(3) 7.2g magnesium hydroxide and 4g concentration are that the formic acid of 99w% joins in the 150g water, and heated and stirred makes it abundant dissolving, solution b2.
(4) get the 31g ammonium molybdate, the 13g cobaltous carbonate, the 17g citric acid, adding 200ml concentration is the ammoniacal liquor of 14w%, stirring and dissolving.Be that 58% ammoniacal liquor and water purification transfer to 9 with the pH value of solution value with concentration then, liquor capacity is 260ml, solution c2.
(5) be that the formic acid of 99w% is dissolved in the 80g water with 4g concentration, solution d2.
(6) solid materials in (1) is mixed with solution a2, b2, c2 and d2, become (mixture pH value is 6) behind the plastic extruded moulding on banded extruder.
(5) the extruded moulding material is at room temperature placed a night.
(6) by (5) gained material under 600 ℃, roasting 3 hours, catalyzer C2.
Embodiment 3
(1) takes by weighing 50g by aluminum hydroxide solid elastomer powder and 500g V250 powder and 13g carbon black that first fertilizer plant of Chinese Qilu Petrochemical company produces, mix.
(2) 9.1g boric acid joins 120ml, concentration is in the ammoniacal liquor of 12w%, and heated and stirred is dissolved boric acid fully, gets solution a3.
(3) 8.1g Repone K joins in the 50g water, and heated and stirred makes it abundant dissolving, gets solution b3.
(4) get the 64g ammonium molybdate, the 30g cobaltous carbonate, the 40g citric acid, adding 320ml concentration is the ammoniacal liquor of 14w%, stirring and dissolving.Be that 58% ammoniacal liquor and water purification transfer to the pH value of solution value with concentration then be 10, liquor capacity is 380ml, solution c3.
(5) be that the acetate of 99w% is dissolved in the 100g water with 11g concentration, solution d3.
(6) solid materials in (1) is mixed with solution a3, b3, c3 and d3, become (mixture pH value is 7) behind the plastic extruded moulding on banded extruder.
(7) with the extruded moulding material under 120 ℃, dry 6 hours.
(8) with material after the drying under 650 ℃, roasting 3 hours, catalyzer C3.
Embodiment 4
(1) takes by weighing 800g by aluminum hydroxide solid elastomer powder and 16g carbon black that first fertilizer plant of Chinese Qilu Petrochemical company produces, mix.
(2) 9.1g boric acid joins 110ml, concentration is in the ammoniacal liquor of 12w%, and heated and stirred is dissolved boric acid fully, gets solution a4.
(3) 8.1g Repone K joins in the 50g water, and heated and stirred makes it abundant dissolving, gets solution b4.
(4) get the 64g ammonium molybdate, the 30g cobaltous carbonate, the 40g citric acid, adding 320ml concentration is the ammoniacal liquor of 14w%, stirring and dissolving.Be that 58% ammoniacal liquor and water purification transfer to the pH value of solution value with concentration then be 10, liquor capacity is 380ml, solution c4.
(5) be that the acetate of 99w% is dissolved in the 100g water with 11g concentration, solution d4.
(6) solid materials in (1) is mixed with solution a4, b4, c4 and d4, become (mixture pH value is 7) behind the plastic extruded moulding on banded extruder.
(7) with the extruded moulding material under 120 ℃, dry 6 hours.
(8) with material after the drying under 650 ℃, roasting 3 hours, catalyzer C4.
Comparative example 1
Catalyzer is according to patent US4 in this example, the preparation of 411,824 methods.
(1) the 48g Cobaltous diacetate is added in the 350ml water; (2) with 15ml, concentration is that 88% formic acid joins in the 200ml distilled water; (3) solution in (1) is joined solution in (2), get solution a5; (4) 83gMoO
3Be dissolved in 400ml, concentration and be 14% NH
4In the OH solution, get solution b5.
When temperature was 50 ℃, solution a4 mixed peptization with 850g aluminium hydroxide (with example 1).After solution a5 all adds, continue to mix 20 minutes.Then, the speed adding solution b5 with per minute 50ml after all adding, continues to mix 20 minutes, and the final mixture temperature is 65 ℃.Extrusion then, and 120 ℃ dry 2 hours down, 200 ℃ dry 2 hours down, there are roasting down 1 hour in 680 ℃, water vapor, roasting is 0.5 hour in 680 ℃, air.Get catalyzer C5, its character sees Table 1.
Embodiment 5
Present embodiment has been listed the main physico-chemical property and the evaluation result of above-mentioned each routine catalyzer, referring to table 1, table 2 and table 3.
The main physico-chemical property of table 1 catalyzer
| Catalyzer | ????C1 | ????C2 | ????C3 | ????C4 | ????C5 | ????C6 |
| Surface-area, m 2/ g pore volume, the ml/g mean pore size, the nm pore distribution, % 5-30nm 〉=16nm MoO 3，m％ NiO，m％ CoO，m％ B 2O 3，m％ MgO，m％ K 2O | ????175 ????1.02 ????23? ? ????86 ????54 ????8.7 ????3.0 ????- ????0.5 ????0.5 ????- | ????184 ????1.01 ????21? ? ????90 ????61 ????6.0 ????- ????2.1 ????1.0 ????1.0 ????- | ????155 ????1.04 ????26? ? ????88 ????53 ????9.0 ????- ????3.3 ????2.0 ????- ????2.0 | ????166 ????1.01 ????24? ? ????89 ????58 ????9.2? ? ????2.9 ????2.0 ????- ????2.0 | ????265 ????0.90 ????13? ? ????83 ????10 ????9.1 ????- ????3.1 ????- ????- ????- | ????195 ????0.58 ????11? ? ????- ????- ????16.5 ????6.5 ????- ????1.5 ????- ????- |
Annotate: C6 is that industry contains B catalyst.
Above-mentioned catalyzer is at temperature of reaction 380, reaction pressure 14.7MPa, air speed 1.0h
-1, (under the appreciation condition v), subtract slag with isolated island is that stock oil carries out activity rating to hydrogen-oil ratio 1000, and stability test, and activity rating the results are shown in Table 2, and stability test the results are shown in Table 3.
Table 2 evaluating catalyst result
| Catalyzer | ?C1 | ?C2 | ?C3 | ?C4 | ?C5 | ?C6 |
| Relative reactivity, % take off the S activity and take off (Ni+V) activity | ? ?100 ?100 | ? ?104 ?102 | ? ?101 ?103 | ? ?102 ?102 | ? ?98 ?87 | ? ?102 ?76 |
Table 3 catalyst stability test-results
Table 2 is relative with catalyst impurities in the table 3 remove active in following two formula calculating:
| Catalyzer | 200 hours | 1000 hours | 2000 hours | |
| Desulphurizing activated relatively | ??C1 | ????100 | ????96 | ????94 |
| ??C5 | ????98 | ????85 | ????80 | |
| Relative metal removal activity | ??C1 | ????100 | ????90 | ????85 |
| ??C5 | ????87 | ????77 | ????69 | |
S in the formula (1)
p, S
fBe respectively the content of sulphur in stock oil and the generation oil; S
Pr, S
FrBe respectively stock oil and the content that generates sulphur in the oil when adopting reference catalyst.
M in the formula (2)
p, M
fBe respectively stock oil and generate metals content impurity in the oil; M
Pr, M
FrMetals content impurity in stock oil and the generation oil when being respectively the employing reference catalyst.
As can be seen from Table 1, catalyzer of the present invention is compared with reference catalyst, and pore volume and aperture are bigger, and specific surface area is moderate; The pore volume per-cent height of 〉=16nm.Table 2 evaluation result shows that catalyzer of the present invention has demetalization preferably and desulphurizing activated.Table 3 stability test is the result show, catalyzer of the present invention has better activity stability.
Claims (10)
1, a kind of heavy oil hydrogenation demetal and Hydrobon catalyst, with the aluminum oxide is carrier, contains group vib metal oxide 2-14w% by weight, contains VIII family metal oxide 0.1-8w%, containing boron oxide is 0.1-5w%, and containing IA family or IIA family metal oxide is 0.1-5w%; The pore volume of catalyzer is 0.5-1.3ml/g, and specific surface area is 120-240m
2/ g.
2, according to the described catalyzer of claim 1, it is characterized in that described group vib metal oxide content is 5-10w%, contain VIII family metal oxide 2-4w%, containing boron oxide is 0.5-2w%, containing IA family or IIA family metal oxide is 0.5-2w%; The pore volume of catalyzer is 0.7-1.1ml/g, and specific surface area is 130-190m
2/ g, mean pore size is 8.5～43nm.
3, according to the described catalyzer of claim 2, the mean pore size that it is characterized in that catalyzer is 15～30nm.
4, the described Preparation of catalysts method of a kind of claim 1, its process is: with aluminum oxide with contain group vib metal and VIII family metallic solution, contain IA family or IIA family metallic solution and boron-containing solution, feed intake by claim 1 catalyzer composition, kneading and compacting, dry then, roasting, the preparation catalyzer.
5,, it is characterized in that described aluminum oxide is pseudo-boehmite and/or γ-Al according to the described preparation method of claim 4
2O
3
6,, it is characterized in that described boron-containing solution is the ammonia soln of boric acid according to the described preparation method of claim 4; The described solution that contains group vib and VIII family metal is the citric acid ammonia soln.
7,, it is characterized in that described drying conditions is according to the described preparation method of claim 4: temperature: 80-200 ℃, time 2-8 hour; Described roasting condition is: temperature: 500-800 ℃, and time 0.5-5 hour.
8, according to the described preparation method of claim 5, it is characterized in that described pseudo-boehmite and γ-Al
2O
3Weight ratio be 1: 25-25: 1.
9, according to the described preparation method of claim 4, it is characterized in that described IA family metal is potassium or sodium, its compound is selected from nitrate, carbonate, muriate or oxyhydroxide; IIA family metal is magnesium or calcium, and its compound is selected from muriate, oxyhydroxide, carbonate; The group vib metal is W or Mo, and selected salt is its ammonium salt; VIII family metal is Co or Ni, and selected salt is its nitrate, carbonate, acetate or muriate.
10, according to the described preparation method of claim 4, it is characterized in that in the described kneading process, add polyvinyl alcohol, methylcellulose gum, sesbania powder or carbon black, be as the criterion with alumina content in the material, its content is 1.5-5.5w%.
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| CN101864326A (en) * | 2009-04-15 | 2010-10-20 | 中国石油化工股份有限公司 | Hydrogenation deacidfieation method of acid-containing crude oil |
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| CN102266760A (en) * | 2010-06-03 | 2011-12-07 | 中国石油化工股份有限公司 | Heavy-oil hydrogenating catalyst and application thereof |
| CN102319572A (en) * | 2011-07-08 | 2012-01-18 | 中国石油天然气股份有限公司 | Hydrotreatment catalyst and preparation method thereof |
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| CN102266760B (en) * | 2010-06-03 | 2013-03-06 | 中国石油化工股份有限公司 | Heavy-oil hydrogenating catalyst and application thereof |
| CN102266760A (en) * | 2010-06-03 | 2011-12-07 | 中国石油化工股份有限公司 | Heavy-oil hydrogenating catalyst and application thereof |
| CN102319572B (en) * | 2011-07-08 | 2013-07-31 | 中国石油天然气股份有限公司 | Hydrotreatment catalyst and preparation method thereof |
| CN102319572A (en) * | 2011-07-08 | 2012-01-18 | 中国石油天然气股份有限公司 | Hydrotreatment catalyst and preparation method thereof |
| CN102268285A (en) * | 2011-07-08 | 2011-12-07 | 中国石油天然气股份有限公司 | Pre-hydrotreatment method of reforming feedstocks |
| CN102268285B (en) * | 2011-07-08 | 2013-12-04 | 中国石油天然气股份有限公司 | Pre-hydrotreatment method of reforming feedstocks |
| CN105772006A (en) * | 2014-12-17 | 2016-07-20 | 中国石油化工股份有限公司 | Heavy oil hydrogenation catalyst and application thereof |
| CN105772006B (en) * | 2014-12-17 | 2018-03-20 | 中国石油化工股份有限公司 | A kind of heavy oil hydrogenating treatment catalyst and its application |
| CN107297209A (en) * | 2016-04-16 | 2017-10-27 | 中国石油化工股份有限公司 | A kind of hydrotreating catalyst and preparation method thereof |
| CN107297209B (en) * | 2016-04-16 | 2019-08-06 | 中国石油化工股份有限公司 | A kind of hydrotreating catalyst and preparation method thereof |
| CN108262075A (en) * | 2016-12-30 | 2018-07-10 | 中国石油天然气股份有限公司 | A kind of catalyst for hydrotreatment of residual oil carrier and preparation method thereof |
| CN108262075B (en) * | 2016-12-30 | 2020-12-01 | 中国石油天然气股份有限公司 | Residual oil hydrotreating catalyst carrier and preparation method thereof |
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| Publication number | Publication date |
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| CN1107102C (en) | 2003-04-30 |
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