CN1137245C - Hydrocarbon dearsenicating catalyst and its preparation - Google Patents
Hydrocarbon dearsenicating catalyst and its preparation Download PDFInfo
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- CN1137245C CN1137245C CNB991037634A CN99103763A CN1137245C CN 1137245 C CN1137245 C CN 1137245C CN B991037634 A CNB991037634 A CN B991037634A CN 99103763 A CN99103763 A CN 99103763A CN 1137245 C CN1137245 C CN 1137245C
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Abstract
The present invention discloses a hydrocarbon dearsenicating catalyst and a preparation method thereof. The catalyst is composed of 5 to 25% of MoO3, 2 to 15% of NiO, 0.2 to 4% of P and the balance of a carrier (the carrier is prepared from titanium oxide and proper adhesives). After the adhesives are mixed with hydrous titanium oxide (HTO), sesbania powder and other substances are added to the mixture, and the mixture is shaped in a mixed pugging mode, dried and calcined. Next, a prepared Mo-Ni-P solution is used for soaking or spraying the saturated dipping carrier, and the catalyst is prepared after the saturated dipping carrier is dried and calcined. When the reaction temperature is lowered to 150 DEG C, the catalyst still has high dearsenization activity and has good mechanical strength simultaneously.
Description
The present invention relates to remove the Catalysts and its preparation method of the harmful non-hydrocarbon compound of trace in the hydro carbons.Specifically, be a kind of Catalysts and its preparation method that removes arsenide in the hydro carbons.
Main component is a hydrocarbon compound in the oil, also has some non-hydrocarbons compounds.Wherein some non-hydrocarbon compound is the poisonous substance of catalyst system therefor in the petroleum refining process, and arsenide is exactly wherein a kind of.These arsenides can be present in the fractions such as gasoline, petroleum naphtha, diesel oil and splitting gas, pyrolysis gasoline in petroleum refining process.When the higher fraction of these arsenic content was carried out catalytic reforming or hydrogenation, the existence of arsenide can make reformed or the permanent poisoning of hydrogenation catalyst and inactivation.In order to keep activity of such catalysts and stability, the running period of extension fixture, just must before contain the arsenic fraction, processing carry out raw material and give dearsenification.
Hydrocarbon dearsenicating catalyst and preparation method are more.U.S. Pat 4,046 uses in 674 nickel oxide and molybdenum oxide to be supported on dearsenic catalyst on the aluminum oxide.The temperature of reaction that this catalyzer is had relatively high expectations (being about 288 ℃ and 343 ℃ among the embodiment).Chinese patent CN1,095,749A has introduced and a kind of high-purity hydrogen aluminum oxide and macropore aluminium hydroxide has been mixed and made into carrier, supports the dearsenic catalyst of nickel oxide then.This catalyzer also needs higher temperature of reaction (among the embodiment being 280 ℃).The physical strength of some dearsenic catalysts of industrial use is not high yet, and fragmentation takes place in the running easily, causes catalyst loss, back-mixing and beds obstruction and the reactor internal drop is increased, and influences normal running.
Therefore, the purpose of this invention is to provide a kind of at active high than dearsenification under the low reaction temperatures, that physical strength is good dearsenic catalyst and preparation method thereof.
Dearsenic catalyst of the present invention adopts titanium oxide and tackiness agent to form carrier, and titanium oxide accounts for 60～90% (all in the oxide dry basis weight) of total weight of carrier.Adopt molybdenum, nickel, phosphorus to make catalyst activity component.Catalyzer consists of: 5～25% MoO
3, 2～15% NiO, 0.2～4% P, surplus is carrier (all in a total catalyst weight).
Above-mentioned tackiness agent is aluminium hydroxide, aluminium colloidal sol or silicon sol.
The preparation method of dearsenic catalyst of the present invention is: after earlier hydrous titanium oxide and tackiness agent being mixed, add sesbania powder and nitric acid and/or expanding agent as kneading and compactings such as polyoxyethylene glycol, polyacrylamide, methylcellulose gum or carbon blacks, under 90～130 ℃ of temperature dry 1～6 hour then, in 450～800 ℃ of roasting temperatures 2～8 hours, make carrier again.
Then molybdenum oxide, basic nickel carbonate and phosphoric acid are joined in the deionized water, refluxed 2 hours under 90 ℃ of temperature, make Mo-Ni-P solution.This solution was soaked titanium dioxide carrier 1～8 hour under 30～90 ℃ of temperature; After also this solution can being soaked the method impregnated carrier with spray is saturated, left standstill under the room temperature 0～12 hour.With its under 90～130 ℃ of temperature dry 2～6 hours, in 350～500 ℃ of roastings 2～8 hours, make dearsenic catalyst more then.
Above-mentioned hydrous titanium oxide can be industrial hydrous titanium oxide; Also can be by titanium sulfate or titanyl sulfate and ammoniacal liquor or sodium hydroxide, adopt just add, instead add, and stream or PH swing into any one method in the glue method or several method in conjunction with preparation; Also can prepare by hydrolysis such as tetraisopropoxy titanium or titanium tetrachlorides.
The present invention adopts titanium oxide to add suitable amount of adhesive and makes carrier, and molybdenum, nickel, phosphorus are active constituent, thereby the hydrocarbon dearsenicating catalyst that makes still has higher dearsenification activity when temperature of reaction is low to moderate 150 ℃.Have excellent mechanical intensity simultaneously, its crushing strength 200 newton/centimetre about.
The invention will be further described for the following examples.
Comparative example 1
300 gram SB aluminium hydrate powders add 10 gram sesbania powder, 30 gram polyoxyethylene glycol, 9 milliliter of 65% nitric acid and suitable quantity of water, mixed pinching becomes the bar of 1.6 millimeters of , under 110 ℃ of temperature dry 4 hours, in 550 ℃ of roasting temperatures 4 hours, make carrier r again, its physico-chemical property sees Table 1.
In deionized water, add ammonium molybdate, nickelous nitrate and proper ammonia, wiring solution-forming by following solution composition.Solution composition is 26.5%MoO3,6.5%NiO.200 gram carrier r are immersed in 400 milliliters of above-mentioned solution, and dipping is 2 hours under 40 ℃ of temperature, filters the back under 120 ℃ of temperature dry 4 hours, 480 ℃ of roasting temperatures 4 hours, makes dearsenic catalyst R then, and its physico-chemical property sees Table 2.
Embodiment 1
After industry hydrous titanium oxide 200 grams and SB aluminium hydrate powder 100 grams mix, add 15 gram sesbania powder, 30 gram polyoxyethylene glycol, 15 milliliter of 65% nitric acid and suitable quantity of water, mixed pinching becomes the bar of 1.6 millimeters of , under 110 ℃ of temperature dry 4 hours, in 550 ℃ of roasting temperatures 4 hours, make carrier a again.Its physico-chemical property sees Table 1.
By solution composition, in deionized water, add molybdenum oxide, basic nickel carbonate and phosphoric acid refluxed 2 hours under 90 ℃ of temperature, made Mo-Ni-P solution.Solution composition is 30.0MoO
3Restrain/100 milliliters ,/100 milliliters of 6.5NiO grams ,/100 milliliters of 1.4P grams.200 gram carrier a are immersed in 400 milliliters of above-mentioned solution, soaked 2 hours under 40 ℃ of temperature, filter the back under 110 ℃ of temperature dry 4 hours, in 460 ℃ of roasting temperatures 4 hours, make dearsenic catalyst A again, its physico-chemical property sees Table 2.
Embodiment 2
Use 10%TiO
2Titanium sulfate solution become glue with 15% ammonia soln and stream.Under 40 ℃ of temperature, pH value is controlled at 7.0, continues to feed in raw material 1 hour, stops aging 30 minutes of reinforced back, washing, filtration.Filter cake under 110 ℃ of temperature dry 4 hours grinds the back and crosses 100 mesh sieves.With the above-mentioned xeraphium of 200 grams, add 16 gram sesbania powder, the silicon sol of 200 gram 26%SiO2, mixed pinching becomes the bar of 1.6 millimeters of , under 120 ℃ of temperature dry 4 hours, in 530 ℃ of roasting temperatures 4 hours, makes carrier b again.Its physico-chemical property sees Table 1.
Make dearsenic catalyst B with carrier b by the method for embodiment 1, its physico-chemical property sees Table 2.
Embodiment 3
Use 10%TiO
2Titanium sulfate solution and 12% NaOH solution, carry out PH and swing into glue.Under 90 ℃ of temperature, the pH value hunting range is PH less than 1 to PH9, stops swinging after swinging 4 times.Under 90 ℃ of temperature, wore out 30 minutes washing, filtration then.With the filter cake making beating, add 150 gram SB aluminium hydrate powders then, under 90 ℃ of temperature, stir 20 minutes after-filtration.Filter cake under 110 ℃ of temperature dry 4 hours grinds the back and crosses 100 mesh sieves.With 300 these xeraphiums of gram, add 15 gram sesbania powder, 16 milliliter of 65% nitric acid, mixed pinching becomes the bar of 1.6 millimeters of .Under 110 ℃ of temperature dry 4 hours, in 550 ℃ of roasting temperatures 4 hours, make carrier c again.Its physico-chemical property sees Table 1.
Get 150 gram carrier c, (it consists of: 37.5MoO with 60 milliliters of Mo-Ni-P solution
3Restrain/100 milliliters ,/100 milliliters of 16.3NiO grams ,/100 milliliters of 3.66P grams) carry out saturated spray dipping, left standstill under the room temperature 8 hours.Under 110 ℃ of temperature dry 4 hours, in 440 ℃ of roasting temperatures 4 hours, make dearsenic catalyst C again.Its physico-chemical property sees Table 2.
In addition, also list the physico-chemical property correlation data of A, two commercial catalystss of B in the table 2 in.
The physico-chemical property of table 1, carrier
| Bearer number | Pore volume milliliter/gram | The specific surface meters squared per gram | Crushing strength newton/centimetre |
| r | 0.49 | 290 | 240 |
| a | 0.26 | 166 | 220 |
| b | 0.40 | 157 | 180 |
| c | 0.48 | 145 | 231 |
The physico-chemical property of table 2, catalyzer
| The catalyzer numbering | Bearer number | Pore volume milliliter/gram | The specific surface meters squared per gram | Crushing strength newton/centimetre | Chemical constitution % | ||
| MoO 3 | NiO | P | |||||
| R | r | 0.30 | 230 | 242 | 15 | 5 | |
| A | a | 0.15 | 117 | 228 | 12 | 5 | 1.30 |
| B | b | 0.26 | 113 | 191 | 16 | 5.1 | 1.34 |
| C | c | 0.29 | 105 | 240 | 12 | 5.2 | 1.17 |
| Industry A | Al 2O 3 | 0.35 | 170 | 200 | 23 | ||
| Industry B | Al 2O 3 | 0.46 | 118 | 87 | 25 | ||
Data from table 2 as seen, by the crushing strength of the dearsenic catalyst of the present invention preparation all 200 newton/centimetre about, therefore dearsenic catalyst of the present invention has excellent mechanical intensity.
Embodiment 4
With boiling range is that 35～148 ℃ petroleum naphtha is made stock oil (character sees Table 3), carries out the dearsenification activity test on anti-in that fixed bed is little.Dearsenic catalyst is 1.6MPa in the hydrogen dividing potential drop earlier, and liquid hourly space velocity is 4.0 hours-1, and hydrogen/oil ratio is under the condition of 300 (volume/volume), feeds to contain 2%CS
2Straight-run spirit vulcanize.The sulfuration temperature-rise period is: vulcanized 2 hours under 150 ℃ of temperature earlier, vulcanized 2 hours under 260 ℃ of temperature then, vulcanized 2 hours under 300 ℃ of temperature.After sulfuration finishes, feed stock oil again and under the listed condition of table 4, carry out the dearsenification test.Test-results sees Table 4.
Table 3, stock oil character
| Density (20 ℃) gram per centimeter 3 | Sulphur/nitrogen microgram/gram | Arsenic content ppb | Boiling range | ||||
| IBP | 10％ | 50％ | 90％ | FBP | |||
| 0.7116 | 170/＜2 | 174 | 35.0 | 72.0 | 104.0 | 130.5 | 148.0 |
The dearsenification activity of table 4, catalyzer
| The catalyzer numbering | R | A | B | C | Industry A | Industry B | |
| Pressure, MPa | 2.8 | 2.8 | 2.8 | 2.8 | 2.8 | 2.8 | |
| Temperature, ℃ | 150 | 150 | 150 | 150 | 150 | 150 | |
| Air speed, hour -1 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | 5.0 | |
| Hydrogen/oil, volume/volume | 100 | 100 | 100 | 100 | 100 | 100 | |
| Generate oil and contain arsenic, ppb | 50 | ＜1 | ＜1 | ＜1 | 48 | 26 | |
| Arsenic-removing rate, % | 71.3 | ＞99.4 | ＞99.4 | ＞99.4 | 72.4 | 85.1 | |
Data in the table 4 show, by the dearsenic catalyst of the present invention's preparation, under lower temperature of reaction, compare with domestic and international industrial two kinds of dearsenic catalyst A, B commonly used with comparative catalyst R, and higher dearsenification activity is arranged.
Embodiment 5
With in the straight-run spirit, add arsenic triphenyl in above-mentioned sulfuration, make that arsenic content reaches 500ppm in the oil.Under 180 ℃ of temperature, the hydrogen dividing potential drop is 2.8MPa, and liquid hourly space velocity is 5.0 hours
-1, when hydrogen/oil ratio is 100 (volume/volume), earlier, stop oil-feed after being 2.26% up to deposited arsenic amount on the catalyzer with the bed of this oil by the catalyst A (preparing) vulcanized by example 1.Change to the stock oil in the example 4 then, under the listed reaction conditions of table 5, carry out the dearsenification test again.Testing data sees Table 5
The dearsenification activity of table 5, deposited arsenic rear catalyst
| The catalyzer numbering | Deposited arsenic amount % | Pressure MPa | Temperature ℃ | Air speed hour -1 | Hydrogen/oil volume/volume | Generate oil and contain arsenic ppb | Arsenic-removing rate % |
| A | 2.26 | 2.8 | 200 | 5.0 | 100 | 6 | 96.6 |
Data in the table 5 show that catalyst A still has greater activity when arsenic content is above up to 2%, so catalyst A has higher appearance arsenic ability.
Claims (6)
1. hydrocarbon dearsenicating catalyst is characterized in that: carrier is that titanium oxide and tackiness agent are formed, and titanium oxide accounts for 60～90% of total weight of carrier, all in oxide dry basis weight; Molybdenum, nickel, phosphorus are made the catalyst activity component; Catalyzer consists of: 5～25% MoO
3, 2～1 5% NiO, 0.2～4% P, surplus is a carrier, all in total catalyst weight.
2. according to the described hydrocarbon dearsenicating catalyst of claim 1, it is characterized in that: the tackiness agent in the carrier adopts aluminium hydroxide, aluminium colloidal sol or silicon sol.
3. the preparation method of hydrocarbon dearsenicating catalyst according to claim 1 is characterized in that, comprising:
A) hydrous titanium oxide and tackiness agent are mixed after, add sesbania powder and nitric acid and/or polyoxyethylene glycol, polyacrylamide, methylcellulose gum, carbon black, kneading and compacting, drying is 1～6 hour under 90～130 ℃ of temperature, in 450～800 ℃ of roasting temperatures 2～8 hours, make carrier again;
B) molybdenum oxide, basic nickel carbonate and phosphoric acid are joined in the deionized water, under 90 ℃ of temperature, refluxed 2 hours, make Mo-Ni-P solution;
C) under 30～90 ℃ of temperature, soaked carrier 1～8 hour with Mo-Ni-P solution, or Mo-Ni-P solution left standstill 0～12 hour under the room temperature with saturated the soaking behind the method impregnated carrier of spray, behind carrier immersion or the dipping Mo-Ni-P solution, under 90～130 ℃ of temperature dry 2～6 hours again, 350～500 ℃ of roasting temperatures 2～8 hours, make dearsenic catalyst then.
4. according to the preparation method of the described hydrocarbon dearsenicating catalyst of claim 3, it is characterized in that: hydrous titanium oxide adopts industrial hydrous titanium oxide.
5. according to the preparation method of the described hydrocarbon dearsenicating catalyst of claim 3, it is characterized in that: hydrous titanium oxide is with titanium sulfate or titanyl sulfate and ammoniacal liquor or sodium hydroxide, adopt just add, instead add, and stream or PH swing into any one method or several method combined preparation in the glue method.
6. according to the preparation method of the described hydrocarbon dearsenicating catalyst of claim 3, it is characterized in that: hydrous titanium oxide prepares with tetraisopropoxy titanium or titanium tetrachloride hydrolysis.
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| CNB991037634A CN1137245C (en) | 1999-04-10 | 1999-04-10 | Hydrocarbon dearsenicating catalyst and its preparation |
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| CNB991037634A CN1137245C (en) | 1999-04-10 | 1999-04-10 | Hydrocarbon dearsenicating catalyst and its preparation |
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| CN1137245C true CN1137245C (en) | 2004-02-04 |
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Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1894367A (en) * | 2003-12-19 | 2007-01-10 | 国际壳牌研究有限公司 | Systems, methods, and catalysts for producing a crude product |
| CN1328355C (en) * | 2004-06-04 | 2007-07-25 | 胡泽祥 | Use of colloidal copper in metamorphic jetting fuel regenerating treatment and preparing method thereof |
| CN106215962A (en) * | 2016-08-03 | 2016-12-14 | 浙江大学 | A kind of hydrogenation catalyst co-impregnation liquid and preparation method thereof |
| CN106994351B (en) * | 2017-06-02 | 2019-05-17 | 钦州学院 | A kind of distillate hydrogenation dearsenic catalyst and preparation method |
| CN109589762B (en) * | 2018-12-29 | 2021-09-10 | 沈阳三聚凯特催化剂有限公司 | Gas-phase dearsenic agent and preparation method thereof |
| CN110639466B (en) * | 2019-09-30 | 2020-12-01 | 四川润和催化新材料股份有限公司 | Dearsenic adsorbent and preparation method thereof |
| CN118268001A (en) * | 2022-12-23 | 2024-07-02 | 中国石油天然气股份有限公司 | Hydrogenation dearsenification method and application thereof in gasoline hydrogenation dearsenification |
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