CN103320159B - A kind of method removing mercaptan sulfur in catalytically cracked gasoline - Google Patents
A kind of method removing mercaptan sulfur in catalytically cracked gasoline Download PDFInfo
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Abstract
The present invention relates to a kind of method removing mercaptan sulfur in catalytically cracked gasoline, belong to field of gasoline desulfurization.Remove a method for mercaptan sulfur in catalytically cracked gasoline, be catalyzed reaction, reaction conditions is: reaction pressure is 0.5 ~ 3.0MPa, hydrogen to oil volume ratio 50:1 ~ 600:1, and temperature of reaction is 60 ~ 120 DEG C, and during liquid, volume space velocity is 0.5 ~ 6.0h
-1described catalyzer with aluminum oxide or nano-HZSM-5 zeolite and alumina composite solid acid for carrier, by the mass percent accounting for catalyzer total mass, comprising: zinc oxide 5% ~ 20%, ferric oxide 5% ~ 15%, lanthanum trioxide 0.5% ~ 5%, phosphorus oxide 0.5% ~ 5%.The method low temperature mercaptan sulfur removal activity removing mercaptan sulfur in catalytically cracked gasoline of the present invention is high, and hydrogenation of olefins activity is low, and octane value does not lose substantially.
Description
Technical field
The present invention relates to a kind of method removing mercaptan sulfur in catalytically cracked gasoline, belong to field of gasoline desulfurization.
Background technology
Along with the fast development of automotive industry and the reinforcement gradually of people's environmental consciousness, countries in the world have promulgated new environmental regulation and clean fuel oil standard in succession.In February, 2012, " ambient air quality " that China has issued new revision adds PM2.5 monitoring index.The data display of Chinese Ministry of Environmental Protection, within 2011, Beijing light-duty vehicle discharges oxynitride (NOx) 80.7 ten thousand tons, particulate matter (PM) 6.5 ten thousand tons, 166.2 ten thousand tons, hydrocarbon polymer (HC), carbon monoxide (CO) 1621.7 ten thousand tons, becomes the main source of the urban air pollution things such as Beijing.Simultaneously very little to the contribution of Conversion of energy during S and N burning in gasoline, but generate the SO of severe contamination air
xand NO
x, not only harm humans is healthy, also can cause the disasters such as acid rain.From 2010, China came into effect the state III standard being equivalent to Europe III, and wherein sulphur content is not more than 150ppm, olefin(e) centent is not more than 30%, aromaticity content is not more than 40%, and benzene content is no more than 1%, and this standard also has sizable gap compared with developed country current standards.The state IV standards regulation sulphur content being equivalent to Europe IV is not more than 50ppm, this standard in Beijing, the ground such as Shanghai and Guangzhou takes the lead in implementing.According to " Beijing's clean air action plan " planning, capital V vehicle emission standards is implemented in May, 2012 in Beijing, and provides the fuel oil for vehicles of capital V standard together.The Executive Meeting of the State Council held on February 6th, 2013 clearly proposes will implement in full motor spirit state IV standards the end of the year 2014.And more strict state five gasoline standard (sulphur content is not more than 10ppm) will be issued before the end of the year 2013, end of the year transitional period to 2017.How hydro-upgrading reduces the key that olefin(e) centent in gasoline, reduction loss of octane number, reduction sulphur content and mercaptans content are modifying catalytically cracked gasolines.
Patent EP1031622 discloses the method for a kind of full cut FCC gasoline desulfurization.The first step is by sulfide hydrotreated lube base oil unsaturated in FCC gasoline, is converted into mercaptan sulfur.Saturated sulfide hydrodesulfurizationconversion conversion is hydrogen sulfide by second step again.But mercaptan sulfur during the sulfide remained in the finished product, causes mercaptan sulfur content in product defective.
Patent CN101987970A discloses a kind of method removing mercaptan from gasoline, raw material is introduced by reactor top, from top to bottom flow through reactor, contact under certain operating conditions with the mercaptan-eliminating catalyst loaded in reactor, in raw material, mercaptan decomposition is alkene and hydrogen sulfide.Reactor bottom introduces stripping fluid, and stripping fluid and gasoline counter current contact, shift out reaction zone by the hydrogen sulfide of generation.Stripping fluid containing the hydrogen sulfide device top that responds is discharged, and reactor bottom is drawn and is stripped of the gasoline products of mercaptan.
Patent CN151192A discloses a kind of method removing mercaptan from gasoline.Being send in fixed-bed reactor by the FCC gasoline containing C4 ~ C12 together with appropriate hydrogen, is that mercaptan in gasoline and diolefine react and generate the higher sulfide of boiling point.Reacted product enters in the catalytic distillation tower being filled with mercaptan removal dual-function catalyst, removes the mercaptan in petroleum naphtha, and the sulfide that reaction generates is discharged together with fractionation with last running at the bottom of tower.
Patent CN1024516694A discloses a kind of hydro-sweetening Catalysts and its preparation method and application.Catalyzer for carrier, with copper and zinc for active ingredient, take phosphorus as adjuvant component with aluminum oxide or silicon-containing alumina.This catalyzer adopts once the preparation of saturated dipping technique.Be applicable to carry out the reaction of selective hydrodesulfurization alcohol to light-end products.
Patent CN102125846A describes a kind of mercaptan etherification catalyst.Catalyzer take aluminum oxide as carrier, and modified component is one or more in Be, Mg, Ca, Sr, Ba, La, Ce.Or one or both and Mo in active ingredient oil Fe and Ni form jointly.This catalyzer can be used for removing the mercaptan in catalytic gasoline of whole fraction and diolefine.
Summary of the invention
The object of the present invention is to provide a kind of method removing mercaptan sulfur in catalytically cracked gasoline, the method low temperature mercaptan sulfur removal activity is high, and hydrogenation of olefins activity is low, and octane value does not lose substantially.
Remove a method for mercaptan sulfur in catalytically cracked gasoline, be catalyzed reaction, reaction conditions is: reaction pressure is 0.5 ~ 3.0MPa, hydrogen to oil volume ratio 50:1 ~ 600:1, and temperature of reaction is 60 ~ 120 DEG C, and during liquid, volume space velocity is 0.5 ~ 6.0h
-1,
The catalyzer of described catalyzed reaction, comprising by the mass percent accounting for catalyzer total mass for carrier with aluminum oxide or nano-HZSM-5 zeolite and alumina composite solid acid:
Zinc oxide 5% ~ 20%
Ferric oxide 5% ~ 15%
Lanthanum trioxide 0.5% ~ 5%
Phosphorus oxide 0.5% ~ 5%.
Low temperature hydrodesulfurisation alcohol catalyst provided by the invention is with aluminum oxide or nano-ZSM-5 molecular sieve and alumina composite solid acid for carrier, with ferric oxide and zinc oxide for active ingredient, is the second modified component with lanthanum trioxide and phosphorus oxide.
Of the present inventionly remove the preferred described catalyzer of the method for mercaptan sulfur in catalytically cracked gasoline, by mass percentage, be made up of following component:
Zinc oxide 5% ~ 20%
Ferric oxide 5% ~ 15%
Lanthanum trioxide 0.5% ~ 5%
Phosphorus oxide 0.5% ~ 5%
Nano-HZSM-5 zeolite 0 ~ 20%
Aluminum oxide 55% ~ 89%.
The method removing mercaptan sulfur in catalytically cracked gasoline of the present invention, when described support of the catalyst is aluminum oxide, that the salpeter solution of pseudo-boehmite, sesbania powder and mass concentration 1% ~ 10% is mixed, through kneading, extruded moulding, 35 ~ 120 DEG C of dryings, 500 ~ 600 DEG C of roastings, obtained alumina supporter
The add-on of described sesbania powder is 0.1% ~ 5.0% of pseudo-boehmite butt quality;
The consumption of described nitric acid and the ratio of raw material total amount are 600 ~ 800ml:1kg.
Above-mentioned raw materials refers to sesbania powder and pseudo-boehmite.
The method removing mercaptan sulfur in catalytically cracked gasoline of the present invention, described support of the catalyst be nano-ZSM-5 molecular sieve and alumina composite solid acid time, its preparation method comprises the following steps:
1. nano-ZSM-5 molecular sieve and pseudo-boehmite are mixed in proportion, the salpeter solution adding sesbania powder and mass concentration 1% ~ 10% mixes, through kneading, extruded moulding, 35 ~ 120 DEG C of dryings, 500 ~ 600 DEG C of roastings, obtained nano-ZSM-5 molecular sieve and alumina composite solid acid carrier
The add-on of described sesbania powder is 0.1% ~ 5.0% of nano-ZSM-5 molecular sieve and pseudo-boehmite butt total mass;
The consumption of described nitric acid and the ratio of raw material total amount are 500 ~ 800ml:1kg;
2. the nano-ZSM-5 carrier 1. obtained through step is put into aqueous ammonium nitrate solution, normal temperature dipping 3 times, each 1 hour; After filtration, then use deionized water wash, drying, roasting;
3. the nano-HZSM-5 zeolite 2. obtained through step is put into salpeter solution, normal temperature dipping 24 hours; After filtration, then use deionized water wash, drying, roasting;
4. the nano-HZSM-5 zeolite 3. obtained through step is placed in fixed bed constant temperature zone, passes into water vapor at a given temperature and carry out hydrothermal treatment consists;
Described hydrothermal conditions is: hydrothermal treatment consists temperature 400 ~ 700 DEG C, mass space velocity 0.5 ~ 5h-1, treatment time 1 ~ 10h.
In above-mentioned preparation method, step 1. in, the consumption of described nitric acid and the ratio of raw material total amount are 500 ~ 800ml:1kg, and wherein, raw material refers to nano-ZSM-5 molecular sieve, pseudo-boehmite and sesbania powder.
Step 2. middle drying, roasting condition is: 100 DEG C of dry 12h, 540 DEG C of roasting 4h; The concentration of preferred aqueous ammonium nitrate solution is 0.4mol/L;
Step 3. dry, roasting condition is: 100 DEG C of dry 12h, 540 DEG C of roasting 4h; The concentration of preferred salpeter solution is 0.6mol/L;
The nano-ZSM-5 molecular sieve used in the present invention, can be bought by market, or by publication number be described in the patent of CN1240193 method preparation, namely modulus is adopted to be that the water glass of 3.18 is as silicon source, with analytical pure sulfuric acid aluminium for aluminium source, water is deionized water, and analytically pure sulfuric acid concentration is 98%, organic amine template is chemical pure 70% ethylamine solution or chemical pure propylamine or n-Butyl Amine 99, and gained ZSM-5 molecular sieve grain fineness number is less than 100nm.
Catalyzer of the present invention adopts equal-volume co-impregnation first to introduce support of the catalyst by iron content with containing zinc active ingredient, adopt equal-volume co-impregnation will introduce catalyzer containing lanthanum and phosphorous modified component after drying, roasting again, after drying roasting, obtain final catalyst.
The preparation method removing the method used catalyst of mercaptan sulfur in catalytically cracked gasoline of the present invention preferably includes following processing step:
Iron containing compounds, zinc compound and deionized water are mixed, steeping fluid obtained stable after stirring; By above-mentioned steeping fluid with equi-volume impregnating impregnated carrier 6 ~ 24h, then through 35 ~ 120 DEG C of drying 12 ~ 24h, 500 ~ 650 DEG C of roastings; Then will mix containing lanthanum compound, P contained compound and deionized water, steeping fluid obtained stable after stirring; By steeping fluid with the catalyzer 6 ~ 24h of the above-mentioned roasting of equi-volume impregnating dipping, then through 35 ~ 120 DEG C of drying 12 ~ 24h, 500 ~ 650 DEG C of roastings.
Iron containing compounds described in the present invention, zinc compound are preferably selected from one or more in chlorate, nitrate, vitriol or acetate; Described is lanthanum nitrate containing lanthanum compound; Described P contained compound is preferably selected from one or more in phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate, ammonium phosphate.
In the method for the invention, used catalyst comprises the step of reduction before using, and reduction process is as follows: loaded by catalyzer in reactor, is 0.5 ~ 3.0MPa at reacting system pressure, and hydrogen volume air speed is 50 ~ 600h
-1, temperature is reduction 0.5 ~ 12h at 150 ~ 400 DEG C.
The method low temperature mercaptan sulfur removal activity removing mercaptan sulfur in catalytically cracked gasoline of the present invention is high, and hydrogenation of olefins activity is low, and octane value does not lose substantially.
Embodiment
Following non-limiting example can make the present invention of those of ordinary skill in the art's comprehend, but does not limit the present invention in any way.
In following embodiment, ZSM-5 molecular sieve used is purchased from Dalian University of Science & Engineering Lv Yuan Chemical Co., Ltd., and granularity is 70 ~ 100nm.
Described catalyst components utilizes X-ray fluorescence spectra analysis (XRF) to measure.
The preparation of alumina supporter:
Take 1kg pseudo-boehmite and 25g sesbania powder, mixed, add the salpeter solution 650ml that mass concentration is 10%, shaping in banded extruder after abundant kneading.Room temperature places 12h.Again through 100 DEG C of dry 12h, 540 DEG C of roasting 3h.Obtained alumina supporter.
The preparation of nano-ZSM-5 molecular sieve and alumina composite solid acid carrier:
Take the former powder of 220g nano-ZSM-5 molecular sieve, 1.14kg pseudo-boehmite and 30g sesbania powder, mixed, add the salpeter solution 780ml that mass concentration is 10%, shaping in banded extruder after abundant kneading.Room temperature places 12h.Again through 100 DEG C of dry 12h, 540 DEG C of roasting 3h.
Above-mentioned catalyzer is placed in 0.4mol/L ammonium nitrate solution by solid-to-liquid ratio 1:5, at room temperature places 1h.Deionized water wash is used after filtration.Repeat above operation twice.Through 100 DEG C of dry 12h, 540 DEG C of roasting 3h.
Above-mentioned catalyzer is placed in 0.6mol/L salpeter solution by solid-to-liquid ratio 1:5, at room temperature places 24h.Deionized water wash is used after filtration.Through 100 DEG C of dry 12h, 540 DEG C of roasting 3h.
Said catalyst carrier is filled in fixed bed constant temperature zone, 700 DEG C, air speed 3h-1 passes into steam-treated 3h.Obtain nano-ZSM-5 and alumina composite solid acid carrier.
Embodiment 1
By 11.0g iron nitrate, 4.0g zinc nitrate, deionized water 15ml mixes, and obtains the common steeping fluid of iron content, zinc.20g alumina supporter is flooded 12h with under above-mentioned steeping fluid room temperature.Through 100 DEG C of dry 12h, 540 DEG C of roasting 4h.Again by 0.8g lanthanum nitrate, 0.7g primary ammonium phosphate and the mixing of 15ml deionized water.Above-mentioned catalyzer is placed in steeping fluid 12h.Through 100 DEG C of dry 12h, 540 DEG C of roasting 4h, obtain catalyst A.
Embodiment 2
By 15.1g iron nitrate, 5.0g zinc nitrate, deionized water 15ml mixes, and obtains the common steeping fluid of iron content, zinc.20g alumina supporter is flooded 12h with under above-mentioned steeping fluid room temperature.Through 100 DEG C of dry 14h, 550 DEG C of roasting 4h.Again by 1.1g lanthanum nitrate, 0.5g primary ammonium phosphate and the mixing of 15ml deionized water.Above-mentioned catalyzer is placed in steeping fluid 12h.Through 100 DEG C of dry 16h, 550 DEG C of roasting 6h, obtain catalyst B.
Embodiment 3
By 18.8g iron nitrate, 5.7g zinc nitrate, deionized water 15ml mixes, and obtains the common steeping fluid of iron content, zinc.20g nano-ZSM-5 molecular sieve and alumina composite solid acid carrier are flooded 24h with under above-mentioned steeping fluid room temperature.Through 100 DEG C of dry 16h, 600 DEG C of roasting 5h.Again by 0.5g lanthanum nitrate, 0.4g Secondary ammonium phosphate and the mixing of 15ml deionized water.Above-mentioned catalyzer is placed in steeping fluid 24h.Through 100 DEG C of dry 16h, 600 DEG C of roasting 5h, obtain catalyzer C.
Comparative example 1
By 13.1g iron nitrate, 4.8g zinc nitrate, deionized water 15ml mixes, and obtains the common steeping fluid of iron content, zinc.20g alumina supporter is flooded 12h with under above-mentioned steeping fluid room temperature.Through 100 DEG C of dry 14h, 550 DEG C of roasting 4h.Obtain comparative example catalyzer D.
Comparative example 2
By 14.3g iron nitrate, 5.6g zinc nitrate, deionized water 15ml mixes, and obtains the common steeping fluid of iron content, zinc.20g nano-ZSM-5 molecular sieve and alumina composite solid acid carrier are flooded 24h with under above-mentioned steeping fluid room temperature.Through 100 DEG C of dry 16h, 540 DEG C of roasting 4h, obtain comparative example catalyzer E.
Table 1 catalyzer of the present invention and comparative example catalyzer materialization composition
The mercaptan removal that small fixed reactor is investigated above-mentioned catalyzer is active.Loaded catalyst 2.2g.First logical hydrogen reducing.Hydrogen flowing quantity is 20ml/min.Hydrogen pressure 1.0MPa.Reduction temperature is 250 DEG C, constant temperature reduction 12h.After reduction, temperature is down to 70 DEG C, and reactor keeps 70 DEG C, passes into full cut FCC gasoline, and reaction pressure is 1.0MPa, and gasoline-volume air speed is 3.0h
-1, hydrogen-oil ratio is 200:1.Table 2 lists the main character of raw material and each catalyzer 200h product.
Table 2 stock oil and 200h product property
As can be seen from Table 2, mercaptan sulfur in stock oil, under temperature of reaction is the condition of 70 DEG C, can be down to below 1.5ppm from 37.8ppm by the mercaptan-eliminating catalyst prepared according to the inventive method, and loss of octane number is less than 0.1 unit, and mercaptan removal sulphur rate reaches 96%.Comparative example catalyzer is when operating 200h, and in product, mercaptan sulfur content is about 15ppm, illustrates that in the present invention, the second modified component can improve the mercaptan removal sulphur activity of catalyzer.
Embodiment 4
The present embodiment investigates catalyst A reactive behavior stability, reductive condition and reaction conditions the same.Table 3 is raw material and each step of reaction product property.
Table 3 stock oil and each step of reaction product property of catalyst A
As can be seen from the reaction result of table 3, when reaction 200h, 500h and 1000h, in product, mercaptan sulfur content is respectively 1.1ppm, 0.9ppm and 1.2ppm.Mercaptan sulfur content, without obvious ascendant trend, illustrates that catalyzer prepared by the present invention has good low temperature and removes mercaptan sulfur reactive behavior and stability.
Claims (9)
1. remove a method for mercaptan sulfur in catalytically cracked gasoline, be catalyzed reaction, reaction conditions is: reaction pressure is 0.5 ~ 3.0MPa, hydrogen to oil volume ratio 50:1 ~ 600:1, and temperature of reaction is 60 ~ 120 DEG C, and during liquid, volume space velocity is 0.5 ~ 6.0h
-1,
The catalyzer of described catalyzed reaction, comprising by the mass percent accounting for catalyzer total mass for carrier with aluminum oxide or nano-HZSM-5 zeolite and alumina composite solid acid:
2. method according to claim 1, is characterized in that: described catalyzer, by mass percentage, is made up of following component:
3. method according to claim 1, it is characterized in that: when described support of the catalyst is aluminum oxide, that the salpeter solution of pseudo-boehmite, sesbania powder and mass concentration 1% ~ 10% is mixed, through kneading, extruded moulding, 35 ~ 120 DEG C of dryings, 500 ~ 600 DEG C of roastings, obtained alumina supporter
The add-on of described sesbania powder is 0.1% ~ 5.0% of pseudo-boehmite butt quality;
The consumption of described nitric acid and the ratio of raw material total amount are 600 ~ 800ml:1kg.
4. method according to claim 1, is characterized in that: described support of the catalyst be nano-ZSM-5 molecular sieve and alumina composite solid acid time, its preparation method comprises the following steps:
1. nano-ZSM-5 molecular sieve and pseudo-boehmite are mixed in proportion, the salpeter solution adding sesbania powder and mass concentration 1% ~ 10% mixes, through kneading, extruded moulding, 35 ~ 120 DEG C of dryings, 500 ~ 600 DEG C of roastings, obtained nano-ZSM-5 molecular sieve and alumina composite solid acid carrier
The add-on of described sesbania powder is 0.1% ~ 5.0% of nano-ZSM-5 molecular sieve and pseudo-boehmite butt total mass;
The consumption of described nitric acid and the ratio of raw material total amount are 500 ~ 800ml:1kg;
2. the nano-ZSM-5 carrier 1. obtained through step is put into aqueous ammonium nitrate solution, normal temperature dipping 3 times, each 1 hour; After filtration, then use deionized water wash, drying, roasting;
3. the nano-HZSM-5 zeolite 2. obtained through step is put into salpeter solution, normal temperature dipping 24 hours; After filtration, then use deionized water wash, drying, roasting;
4. the nano-HZSM-5 zeolite 3. obtained through step is placed in fixed bed constant temperature zone, passes into water vapor at a given temperature and carry out hydrothermal treatment consists;
Described hydrothermal conditions is: hydrothermal treatment consists temperature 400 ~ 700 DEG C, mass space velocity 0.5 ~ 5h
-1, treatment time 1 ~ 10h.
5. method according to claim 1, is characterized in that: described catalyzer is prepared as follows:
Iron containing compounds, zinc compound and deionized water are mixed, steeping fluid obtained stable after stirring; By above-mentioned steeping fluid with equi-volume impregnating impregnated carrier 6 ~ 24h, then through 35 ~ 120 DEG C of drying 12 ~ 24h, 500 ~ 650 DEG C of roastings; Then will mix containing lanthanum compound, P contained compound and deionized water, steeping fluid obtained stable after stirring; By steeping fluid with the catalyzer 6 ~ 24h of the above-mentioned roasting of equi-volume impregnating dipping, then through 35 ~ 120 DEG C of drying 12 ~ 24h, 500 ~ 650 DEG C of roastings.
6. method according to claim 5, is characterized in that: described iron containing compounds, zinc compound are selected from one or more in chlorate, nitrate, vitriol or acetate.
7. method according to claim 5, is characterized in that: described is lanthanum nitrate containing lanthanum compound.
8. method according to claim 5, is characterized in that: described P contained compound is selected from one or more in phosphoric acid, primary ammonium phosphate, Secondary ammonium phosphate, ammonium phosphate.
9. method according to claim 1, is characterized in that: catalyzer comprises the step of reduction before using, reduction process is as follows: loaded by catalyzer in reactor, is 0.5 ~ 3.0MPa at reacting system pressure, and hydrogen volume air speed is 50 ~ 600h
-1, temperature is reduction 0.5 ~ 12h at 150 ~ 400 DEG C.
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| WO2015046345A1 (en) * | 2013-09-27 | 2015-04-02 | コスモ石油株式会社 | Hydrogenation catalyst for heavy hydrocarbon oil, production method for hydrogenation catalyst for heavy hydrocarbon oil, and hydrogenation method for heavy hydrocarbon oil |
| CN106925338B (en) * | 2015-12-30 | 2020-01-07 | 中国石油天然气股份有限公司 | Sulfur-carrying type hydrodesulfurization modification catalyst and preparation method thereof |
| CN106929091B (en) * | 2015-12-30 | 2019-04-05 | 中国石油天然气股份有限公司 | A kind of catalytic gasoline hydrogenation desulfurization method for modifying |
| CN107583660B (en) * | 2016-07-07 | 2020-01-07 | 中国石油天然气股份有限公司 | Hydrodesulfurization catalyst containing zinc-aluminum layered material and preparation method thereof |
| CN112090442A (en) * | 2020-09-24 | 2020-12-18 | 天长市润源催化剂有限公司 | Desulfurization catalyst with modified ZSM-5 molecular sieve as carrier and preparation method thereof |
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| CN1508224A (en) * | 2002-12-19 | 2004-06-30 | 中国石油化工股份有限公司 | Hydrocracking after-treatment catalyst and preparing method thereof |
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| CN102125846A (en) * | 2010-12-24 | 2011-07-20 | 中国石油大学(北京) | Mercaptan etherification catalyst |
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| CN1508224A (en) * | 2002-12-19 | 2004-06-30 | 中国石油化工股份有限公司 | Hydrocracking after-treatment catalyst and preparing method thereof |
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| CN102451694A (en) * | 2010-10-15 | 2012-05-16 | 中国石油化工股份有限公司 | Hydrogenation dethiolizing catalyst, preparation method thereof and application thereof |
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| GB2551118A (en) * | 2016-05-31 | 2017-12-13 | Univ Oxford Innovation Ltd | Process |
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