CN108855115A - A kind of coated catalysts and preparation method and application - Google Patents
A kind of coated catalysts and preparation method and application Download PDFInfo
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- CN108855115A CN108855115A CN201810568061.6A CN201810568061A CN108855115A CN 108855115 A CN108855115 A CN 108855115A CN 201810568061 A CN201810568061 A CN 201810568061A CN 108855115 A CN108855115 A CN 108855115A
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/85—Chromium, molybdenum or tungsten
- B01J23/88—Molybdenum
- B01J23/883—Molybdenum and nickel
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0222—Compounds of Mn, Re
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/024—Compounds of Zn, Cd, Hg
- B01J20/0244—Compounds of Zn
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/0203—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of metals not provided for in B01J20/04
- B01J20/0248—Compounds of B, Al, Ga, In, Tl
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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Abstract
A kind of coated catalysts, it is characterised in that including hydrodesulfurization activity component, sulfur absorbent and carrier three parts, hydrodesulfurization activity constituent mass score is 2.0-20.0wt%, and sulfur absorbent mass fraction is 30.0-80.0wt%, and surplus is carrier.With handling without reduction or presulfurization, catalyst is gone into operation at low cost the present invention using simplicity；The advantage of Sulfur capacity higher than common absorbing desulfurization catalyst 10% or more.
Description
Technical field
The present invention relates to a kind of reaction absorbing desulfurization catalysts and preparation method thereof, specifically a kind of for reacting absorption
The coated catalysts and preparation method and application of desulfurization.
Technical background
Organic sulfur in fuel oil can be done great harm to the environment after burning, and countries in the world have been formulated strictly thus
Laws and regulations limit the sulfur content in fuel oil.In recent years, the environment worsening for reply, China's gasoline quality standard will be complete
State four standard is carried out in face, and sulfur content in oil products decreases below 50ppm from the 150ppm that is less than of three standard of state, reduces by 67%.And Beijing
Districts and cities, the gasoline quality standards such as Guangzhou, the Shenzhen in the districts and cities such as city, the Nanjing in Shanghai and Jiangsu, Suzhou, Wuxi and Guangdong are up to
Five standard of state, sulfur content in oil products decreases below 10ppm from the 50ppm that is less than of state four standard, then reduces by 80%.
For the gasoline in China mainly from catalytic cracking, sulfur content of catalytic cracking gasoline is high, it is necessary to could use by desulfurization.
The method of the desulfurization of fuel oil has two kinds of desulfurization of hydrofinishing and absorption at present, but hydrofinishing needs to consume a large amount of hydrogen,
It is at high cost, and alkene can be made to be saturated, reduce the octane number of gasoline.For diesel oil, although hydrofinishing can improve 16
Alkane value, but hydrogen consumption cost is too high.Therefore a kind of relatively small process for deep desulphurization of hydrogen gas consumption is needed, reduction is produced into
This.
Concophillips Company of the U.S. develops a kind of S-Zorb absorption desulfurization technology, the technology at 243-413 DEG C of temperature,
Pressure 0.7-1.2MPa, air speed 4-10h-1, face under hydrogen and fluidization conditions and adsorb desulfurization, then make to inhale by the method for oxygen enrichment regeneration
Attached dose of regeneration, adsorbent are mainly made of active component nickel oxide and adsorbent zinc oxide.Company is again right in US7182918B2
The technology is improved.In order to improve the intensity of catalyst and reduce aromatic hydrocarbons loss, the activity of the catalyst is lower, needs frequency
Numerous regeneration.
CN1048418, CN1151333 disclose one kind and contain zinc oxide, silica, colloidal oxide and promotor
New compositions, improve pore volume and specific surface area by the way that pore creating material is added in colloid, but the catalysis of this method preparation
Agent intensity is poor.
CN1130253C and US6150300 discloses a kind of comprising zinc oxide, silica, aluminium oxide, reduced state nickel or cobalt
Mixture granular adsorbent composition, zinc oxide and aluminium oxide, silica are first prepared into pelleted substrate, then
Nickel-loaded, and provide the application method of the catalyst.The process is comparatively laborious, and carrier is catalyzed after nickel-loaded by roasting
The decline of agent intensity is serious, easily causes dusting.
The problems such as that there is Sulfur capacity is small using zinc oxide as the catalyst of adsorbent at present, catalyst frequent regeneration.Therefore have
Necessity develops a kind of novel adsorption desulphurization catalyst, improves these performances, to meet production requirement.
Summary of the invention
Small for current reaction absorbing desulfurization catalyst Sulfur capacity, later period desulphurizing activated decline is significant in the reaction, catalyst
The problems such as frequent regeneration, the object of the present invention is to provide a kind of coating structure catalyst to promote its Sulfur capacity and middle and later periods desulphurizing ability
The coated catalysts and preparation method and application of energy.
Catalyst of the present invention includes hydrodesulfurization activity component, sulfur absorbent and carrier three parts, hydrodesulfurization activity
Constituent mass score is 2.0-20.0wt%, and sulfur absorbent mass fraction is 30.0-80.0wt%, and surplus is carrier.
The hydrodesulfurization activity component is made of AB two parts, A：B molar ratio is 0.1-10, and A is nickel oxide, oxygen
Change at least one of cobalt, B is at least one of molybdenum oxide, tungsten oxide.
The sulfur absorbent is at least one of zinc oxide, manganese oxide, iron oxide, calcium oxide, and the carrier is oxidation
At least one of silicon, aluminium oxide, molecular sieve.
Catalyst of the present invention has two coatings of A and B, obtains specific layer structure by special infusion process, specifically
Preparation method be：
(1) sulfur absorbent or its predecessor, carrier or its predecessor and promotor kneading is uniform, extruded moulding；
(2) by sample drying obtained by step (1), 100-150 is increased to from room temperature with the heating rate of 10-20 DEG C/min when dry
DEG C, 6-24h is dried at this temperature；
(3) sample obtained by step (2) is roasted into 3-12h at 400-600 DEG C；
(4) B component predecessor is made into the solution that concentration is 0.05-1mol/L；
(5) step (4) acquired solution is added in sample obtained by step (3) and impregnates 2-20h, sample filtering is dry, when dry
It is increased to 100-150 DEG C from room temperature with the heating rate of 10-20 DEG C/min, dries 6-24h at this temperature；
(6) sample obtained by step (5) is roasted into 3-12h at 400-600 DEG C；
7）Component A predecessor is made into the solution that concentration is 0.05-1mol/L；
(8) step (7) acquired solution is added in sample obtained by step (6) and impregnates 2-20h, sample filtering is dry, when dry
It is increased to 100-150 DEG C from room temperature with the heating rate of 10-20 DEG C/min, dries 6-24h at this temperature；
(9) sample obtained by step (8) is roasted into 3-12h at 400-600 DEG C up to required catalyst.
Wherein, step (1) the sulfur absorbent predecessor is the hydroxide or carbonate of sulfur absorbent.Carrier predecessor
For the hydroxide of carrier.Promotor is sesbania powder or soluble starch, and additional amount is the 0.5-10wt% of sulfur absorbent.
Step (4) the B component predecessor is the ammonium salt of B component；
Step (7) component A predecessor is the nitrate of component A.
Catalyst of the present invention is suitable for the industrial chemicals desulfurization process of sulfur-bearing, and raw material includes gas and liquid form.Especially
Desulfurization is adsorbed in reaction suitable for liquid oil, needs not move through the activation sides such as reduction or presulfurization the characteristics of the catalyst
Formula simplifies pretreatment process, and the curtailment of operation saves catalyst use cost.After reaction temperature is increased to 200-500 DEG C
Directly charging reaction, reaction pressure 0.1-10.0MPa, fuel oil quality air speed are 0.2-5.0h-1, H2/ oil volume ratio is 10-
600。
Advantages of the present invention
A kind of coating structure provided by the invention reacts absorbing desulfurization catalyst, and advantage is：The catalyst is without reduction or in advance
Vulcanizing treatment, catalyst are gone into operation at low cost using simplicity；Sulfur capacity is higher than common absorbing desulfurization catalyst by 10% or more.
Specific embodiment
The present invention is further illustrated with following example, but invention is not intended to be limited thereto.Raw material sulphur of the embodiment of the present invention contains
Amount is 500ppm.
Embodiment 1：
Catalyst preparation：1）30g zinc oxide is taken, 50g manganese oxide, 18g aluminium oxide, 0.04g soluble starch is uniformly mixed, mixed
Pinch into dough, extruded moulding.2）Gained sample is slowly raised 100 DEG C from room temperature with the heating rate of 10 DEG C/min, herein
At a temperature of dry 6h.3）3h is roasted at 400 DEG C obtains bar shaped sample.4）2.23g ammonium heptamolybdate is taken, addition deionized water makes molten
Liquid product is 80ml, and Molybdenum in Solution concentration is 0.149mol/L.5）Acquired solution is added in bar shaped sample and impregnates 2h, by sample
Filtration drying is slowly raised 110 DEG C from room temperature with the heating rate of 12 DEG C/min when dry, dries 6h at this temperature.6）
Gained sample roasts 3h at 400 DEG C.7）0.70g nickel nitrate is taken, the solution that concentration is 0.05mol/L is made into.8）By step 7)
Step 6 is added in acquired solution）2h is impregnated in gained sample, sample filtering is dry, from room temperature with the liter of 15 DEG C/min when dry
Warm rate is slowly raised 100 DEG C, dries 6h at this temperature.9）Sample obtained by step 8) is roasted into 3h at 400 DEG C to obtain the final product
Required catalyst.
By above-mentioned gained catalyst breakage at 20-40 mesh, takes 2.0g catalyst loaded in fixed bed reactors, be warming up to
Directly charging reaction after 200 DEG C.Reaction pressure 0.1MPa, fuel oil quality air speed are 0.2h-1, H2/ oil volume ratio is 10.Catalysis
Agent composition as shown in table 1, reaction condition and the results are shown in Table 2.
Embodiment 2
Catalyst preparation：1）Take 20g calcium oxide, 14.9g iron hydroxide, 25g aluminium oxide, 75g dioxide-containing silica be 33% can
Dissolubility silica solution, 3g sesbania powder are uniformly mixed, extruded moulding.2）By gained sample from room temperature with the heating rate of 20 DEG C/min
150 DEG C are slowly raised, is dried at this temperature for 24 hours.3）12h is roasted at 600 DEG C obtains bar shaped sample.4）Take 19.46g inclined
Ammonium tungstate, deionized water, which is added, makes liquor capacity 45ml, and tungsten concentration is 1.21mol/L in solution.5）Acquired solution is added
20h is impregnated in bar shaped sample, sample filtering is dry, it is slowly raised when dry from room temperature with the heating rate of 10 DEG C/min
It 150 DEG C, dries at this temperature for 24 hours.6）Gained sample roasts 12h at 600 DEG C.7）6.31g cobalt nitrate is taken, being made into concentration is
The solution of 1mol/L.Step 6 is added in step 7) acquired solution）20h is impregnated in gained sample, sample filtering is dry, it is dry
When from room temperature with the heating rate of 20 DEG C/min be slowly raised 150 DEG C, at this temperature it is dry for 24 hours.9）It will be obtained by step 8)
Sample roasts 12h at 600 DEG C up to required catalyst.
By above-mentioned gained catalyst breakage at 20-40 mesh, takes 2.0g catalyst loaded in fixed bed reactors, be warming up to
Directly charging reaction after 500 DEG C.Reaction pressure 5.0MPa, fuel oil quality air speed are 5.0h-1, H2/ oil volume ratio is 600.It urges
Agent composition as shown in table 1, reaction condition and the results are shown in Table 2.
Embodiment 3
Catalyst preparation：1）Take 20g calcium oxide, 10g iron oxide, 30.8g zinc carbonate, 20g aluminium oxide, 30g dioxide-containing silica
For 33% soluble silicon colloidal sol, 10gSBA15 molecular sieve, 5g sesbania powder is uniformly mixed, extruded moulding.2）By gained sample from
Room temperature is slowly raised 140 DEG C with the heating rate of 18 DEG C/min, dries 12h at this temperature.3）6h is roasted at 400 DEG C to obtain
To bar shaped sample.4）4.28g ammonium metatungstate is taken, deionized water, which is added, makes liquor capacity 65ml, and tungsten concentration is in solution
0.33mol/L.5）Acquired solution is added in bar shaped sample and impregnates 10h, sample filtering is dry, from room temperature with 11 when dry
DEG C/heating rate of min is slowly raised 120 DEG C, 12h is dried at this temperature.6）Gained sample roasts 6h at 400 DEG C.
7）13.62g nickel nitrate is taken, 8.77g cobalt nitrate is made into the solution that concentration is 0.8mol/L.8）Step 7) acquired solution is added
Step 6）10h is impregnated in gained sample, sample filtering is dry, it is slowly risen when dry from room temperature with the heating rate of 13 DEG C/min
Height dries 12h to 120 DEG C at this temperature.9）Sample obtained by step 8) is roasted into 6h at 400 DEG C up to required catalyst.
By above-mentioned gained catalyst breakage at 20-40 mesh, takes 2.0g catalyst loaded in fixed bed reactors, be warming up to
Directly charging reaction after 400 DEG C.Reaction pressure 3.0MPa, fuel oil quality air speed are 4.0h-1, H2/ oil volume ratio is 300.It urges
Agent composition as shown in table 1, reaction condition and the results are shown in Table 2.
Embodiment 4
Catalyst preparation：1）Take 20g manganese oxide, 10g calcium oxide, 50g zinc oxide, 5g aluminium oxide, 5gZSM5 molecular sieve, the field 4g
Cyanines powder is uniformly mixed, extruded moulding.2）Gained sample is slowly raised 130 DEG C from room temperature with the heating rate of 16 DEG C/min,
10h is dried at this temperature.3）8h is roasted at 450 DEG C obtains bar shaped sample.4）Take 2.67g ammonium metatungstate, 3.07g molybdic acid
Ammonium, deionized water, which is added, makes liquor capacity 85ml, and Molybdenum in Solution tungsten total concentration is 0.28mol/L.5）Acquired solution is added
8h is impregnated in bar shaped sample, sample filtering is dry, 110 are slowly raised from room temperature with the heating rate of 14 DEG C/min when dry
DEG C, 8h is dried at this temperature.6）Gained sample roasts 8h at 450 DEG C.7）19.45g nickel nitrate is taken, being made into concentration is
The solution of 0.7mol/L.8）Step 6 is added in step 7) acquired solution）8h is impregnated in gained sample, sample filtering is dry, it does
110 DEG C are slowly raised from room temperature with the heating rate of 10 DEG C/min when dry, dries 8h at this temperature.9）It will be obtained by step 8)
Sample roasts 8h at 450 DEG C up to required catalyst.
By above-mentioned gained catalyst breakage at 20-40 mesh, takes 2.0g catalyst loaded in fixed bed reactors, be warming up to
Directly charging reaction after 450 DEG C.Reaction pressure 10.0MPa, fuel oil quality air speed are 3.0h-1, H2/ oil volume ratio is 200.It urges
Agent composition as shown in table 1, reaction condition and the results are shown in Table 2.
Embodiment 5
Catalyst preparation：1）20g manganese oxide is taken, 10g calcium oxide, 45g zinc oxide, 5g aluminium oxide, 3g sesbania powder is uniformly mixed,
Extruded moulding.2）Gained sample is slowly raised 130 DEG C from room temperature with the heating rate of 16 DEG C/min, is dried at this temperature
10h.3）8h is roasted at 450 DEG C obtains bar shaped sample.4）2.67g ammonium metatungstate is taken, deionized water is added in 3.07g ammonium molybdate
Make liquor capacity 85ml, Molybdenum in Solution tungsten total concentration is 0.28mol/L.5）Acquired solution is added in bar shaped sample and is impregnated
5h, sample filtering is dry, 120 DEG C are slowly raised from room temperature with the heating rate of 16 DEG C/min when dry, at this temperature
Dry 9h.6）Gained sample roasts 11h at 440 DEG C.7）19.45g nickel nitrate is taken, the solution that concentration is 0.7mol/L is made into.
8）Step 6 is added in step 7) acquired solution）7h is impregnated in gained sample, sample filtering is dry, from room temperature with 17 when dry
DEG C/heating rate of min is slowly raised 140 DEG C, 7h is dried at this temperature.9）By sample obtained by step 8) at 410 DEG C
8h is roasted up to required catalyst.
By above-mentioned catalyst breakage at 20-40 mesh, takes 2.0g catalyst loaded in fixed bed reactors, be warming up to 250 DEG C
Directly charging reaction afterwards.Reaction pressure 7.0MPa, fuel oil quality air speed are 2.0h-1, H2/ oil volume ratio is 100.Reaction condition
And the results are shown in Table 2.
Embodiment 6
Catalyst preparation：1）Take 10g manganese oxide, 18g calcium oxide, 24.4g zinc hydroxide, 10g ferrous oxide, 20g aluminium oxide,
10g silica, 1g starch are uniformly mixed, extruded moulding.2）Gained sample is slow with the heating rate of 13 DEG C/min from room temperature
110 DEG C are increased to, dries 5h at this temperature.3）3h is roasted at 450 DEG C obtains bar shaped sample.4）5.35g ammonium metatungstate is taken,
2.45g ammonium molybdate, deionized water, which is added, makes liquor capacity 100ml, and Molybdenum in Solution tungsten total concentration is 0.355mol/L.5）By institute
It obtains solution and is added in bar shaped sample and impregnate 4h, sample filtering is dry, it is slow with the heating rate of 14 DEG C/min from room temperature when dry
Slowly 130 DEG C are increased to, dry 10h at this temperature.6）Gained sample roasts 10h at 420 DEG C.7）13.63g nickel nitrate is taken,
It is made into the solution that concentration is 0.2mol/L.8）Step 6 is added in step 7) acquired solution）6h is impregnated in gained sample, by sample
Filtration drying is slowly raised 120 DEG C from room temperature with the heating rate of 14 DEG C/min when dry, dries 8h at this temperature.9）
Sample obtained by step 8) is roasted into 5h at 400 DEG C up to required catalyst.
By above-mentioned catalyst breakage at 20-40 mesh, takes 2.0g catalyst loaded in fixed bed reactors, be warming up to 280 DEG C
Directly charging reaction afterwards.Reaction pressure 2.0MPa, fuel oil quality air speed are 2.0h-1, H2/ oil volume ratio is 100.Reaction condition
And the results are shown in Table 2.
Embodiment 7
Catalyst preparation：1）20g zinc oxide is taken, 40g calcium oxide, 25gMCM-41 molecular sieve, 2g soluble starch is uniformly mixed,
Kneading is at dough, extruded moulding.2）Gained sample is slowly raised 110 DEG C from room temperature with the heating rate of 11 DEG C/min,
Dry 8h at a temperature of this.3）5h is roasted at 420 DEG C obtains bar shaped sample.4）10.69g ammonium metatungstate is taken, deionized water is added
Make liquor capacity 90ml, tungsten concentration is 0.28mol/L in solution.5）Acquired solution is added in bar shaped sample and impregnates 3h, it will
Sample filtering is dry, is slowly raised 130 DEG C from room temperature with the heating rate of 16 DEG C/min when dry, dries at this temperature
7h.6）Gained sample roasts 6h at 400 DEG C.7）19.46g nickel nitrate is taken, the solution that concentration is 0.9mol/L is made into.8）It will step
Step 6 is added in rapid 7) acquired solution）4h is impregnated in gained sample, sample filtering is dry, from room temperature with 14 DEG C/min when dry
Heating rate be slowly raised 140 DEG C, at this temperature dry 6h.9）Sample obtained by step 8) is roasted into 5h at 410 DEG C
Up to required catalyst.
By above-mentioned catalyst breakage at 20-40 mesh, takes 2.0g catalyst loaded in fixed bed reactors, be warming up to 300 DEG C
Directly charging reaction afterwards.Reaction pressure 2.0MPa, fuel oil quality air speed are 2.0h-1, H2/ oil volume ratio is 100.Reaction condition
And the results are shown in Table 2.
Embodiment 8
Catalyst preparation：1）40g zinc oxide is taken, 30g calcium oxide, 15g silica, 1.6g soluble starch is uniformly mixed, mixed
Pinch into dough, extruded moulding.2）Gained sample is slowly raised 140 DEG C from room temperature with the heating rate of 15 DEG C/min, herein
At a temperature of dry 5h.3）11h is roasted at 400 DEG C obtains bar shaped sample.4）9.81g ammonium metatungstate is taken, deionized water, which is added, to be made
Liquor capacity is 70ml, and tungsten concentration is 0.79mol/L in solution.5）Acquired solution is added in bar shaped sample and impregnates 4h, by sample
Product filtration drying is slowly raised 140 DEG C from room temperature with the heating rate of 13 DEG C/min when dry, dries 9h at this temperature.
6）Gained sample roasts 8h at 400 DEG C.7）24.55g nickel nitrate is taken, the solution that concentration is 0.5mol/L is made into.8）By step
7) step 6 is added in acquired solution）6h is impregnated in gained sample, sample filtering is dry, from room temperature with 12 DEG C/min's when dry
Heating rate is slowly raised 120 DEG C, dries 6h at this temperature.9）Sample obtained by step 8) is roasted 6h at 430 DEG C is
Catalyst needed for obtaining.
By above-mentioned catalyst breakage at 20-40 mesh, takes 2.0g catalyst loaded in fixed bed reactors, be warming up to 320 DEG C
Directly charging reaction afterwards.Reaction pressure 2.0MPa, fuel oil quality air speed are 2.0h-1, H2/ oil volume ratio is 100.Reaction condition
And the results are shown in Table 2.
Comparative example 1
Comparative catalyst's preparation：1）Take 20g manganese oxide, 10g calcium oxide, 55g zinc oxide, 5g aluminium oxide, 15g dioxide-containing silica
For 33% soluble silicon colloidal sol, 5gZSM5 molecular sieve, 2g sesbania powder is uniformly mixed.Kneading is at dough, extruded moulding.2）By institute
It obtains sample and is slowly raised 110 DEG C from room temperature with the heating rate of 10 DEG C/min, dry 10h at this temperature.3）At 450 DEG C
Roasting 8h obtains bar shaped sample.4）19.45g nickel nitrate is taken, the solution that concentration is 0.7mol/L is made into.By step 3) acquired solution
Step 4 is added）8h is impregnated in gained sample, sample filtering is dry, it is slow with the heating rate of 10 DEG C/min from room temperature when dry
Slowly 110 DEG C are increased to, dry 8h at this temperature.5）Sample obtained by step 4) is roasted into 8h at 450 DEG C up to required catalysis
Agent.
By above-mentioned gained catalyst breakage at 20-40 mesh, takes 2.0g catalyst loaded in fixed bed reactors, be warming up to
Directly charging reaction after 450 DEG C.Reaction pressure 10.0MPa, fuel oil quality air speed are 3.0h-1, H2/ oil volume ratio is 200.It urges
Agent composition as shown in table 1, reaction condition and the results are shown in Table 2.Compared with Example 4,4 Sulfur capacity of embodiment is implemented than comparison
Example 1 high 15%.
Comparative example 2
Comparative catalyst's preparation：1）Take 20g manganese oxide, 10g calcium oxide, 45g zinc oxide, 5g aluminium oxide, 10g ferrous oxide, 3g
Sesbania powder is uniformly mixed.Kneading is at dough, extruded moulding.2）Gained sample is slow with the heating rate of 15 DEG C/min from room temperature
Slowly 120 DEG C are increased to, dry 15h at this temperature.3）8h is roasted at 440 DEG C obtains bar shaped sample.4）Take 38.91g nitric acid
Nickel is made into the solution that concentration is 0.5mol/L.Step 4 is added in step 3) acquired solution）6h is impregnated in gained sample, by sample
Filtration drying is slowly raised 120 DEG C from room temperature with the heating rate of 10 DEG C/min when dry, dries 7h at this temperature.5）
Sample obtained by step 4) is roasted into 9h at 430 DEG C up to required catalyst.
By 2 catalyst breakage of comparative example at 20-40 mesh, takes 2.0g catalyst loaded in fixed bed reactors, be warming up to 250
Directly charging reaction after DEG C.Reaction pressure 7.0MPa, fuel oil quality air speed are 2.0h-1, H2/ oil volume ratio is 100.React item
Part and the results are shown in Table 2.Comparative example 2 is similar with embodiment 5 catalyst composition, and 5 Sulfur capacity of embodiment is higher than comparison comparative example 2
23%。
Comparative example 3
Comparative catalyst's preparation：1）Take 10g manganese oxide, 18g calcium oxide, 24.4g zinc hydroxide, 10g aluminium oxide, 10g oxidation Asia
Iron, 5g sesbania powder are uniformly mixed.Kneading is at dough, extruded moulding.2）By gained sample from room temperature with the heating speed of 10 DEG C/min
Rate is slowly raised 130 DEG C, dries 12h at this temperature.3）8h is roasted at 420 DEG C obtains bar shaped sample.4）Take 50.58g
Nickel nitrate is made into the solution that concentration is 0.6mol/L.Step 4 is added in step 3) acquired solution）8h is impregnated in gained sample, it will
Sample filtering is dry, is slowly raised 120 DEG C from room temperature with the heating rate of 15 DEG C/min when dry, dries at this temperature
8h.5）Sample obtained by step 4) is roasted into 9h at 450 DEG C up to required catalyst.
By 3 catalyst breakage of comparative example at 20-40 mesh, takes 2.0g catalyst loaded in fixed bed reactors, be warming up to 280
Directly charging reaction after DEG C.Reaction pressure 2.0MPa, fuel oil quality air speed are 2.0h-1, H2/ oil volume ratio is 100.React item
Part and the results are shown in Table 2.Comparative example 3 is similar with embodiment 6 catalyst composition, and 6 Sulfur capacity of embodiment is than comparative example 3 high 17%.
Comparative example 4
Comparative catalyst's preparation：1）40g calcium oxide, 20g zinc oxide, 25gMCM-41,8g sesbania powder are uniformly mixed.Kneading is at face
Group, extruded moulding.2）Gained sample is slowly raised 150 DEG C from room temperature with the heating rate of 15 DEG C/min, at this temperature
Dry 11h.3）8h is roasted at 410 DEG C obtains bar shaped sample.4）58.39g nickel nitrate is taken, being made into concentration is the molten of 0.7mol/L
Liquid.Step 4 is added in step 3) acquired solution）8h is impregnated in gained sample, sample filtering is dry, from room temperature with 14 when dry
DEG C/heating rate of min is slowly raised 140 DEG C, 8h is dried at this temperature.5）By sample obtained by step 4) at 450 DEG C
9h is roasted up to required catalyst.
By 4 catalyst breakage of comparative example at 20-40 mesh, takes 2.0g catalyst loaded in fixed bed reactors, be warming up to 300
Directly charging reaction after DEG C.Reaction pressure 2.0MPa, fuel oil quality air speed are 2.0h-1, H2/ oil volume ratio is 100.React item
Part and the results are shown in Table 2.Comparative example 4 is similar with embodiment 7 catalyst composition, and 7 Sulfur capacity of embodiment is implemented than comparison
Example 4 high 12%.
Comparative example 5
Comparative catalyst's preparation：1）30g calcium oxide, 40g zinc oxide, 15g silica, 2.5g sesbania powder are uniformly mixed.Kneading at
Dough, extruded moulding.2）Gained sample is slowly raised 110 DEG C from room temperature with the heating rate of 11 DEG C/min, in this temperature
Lower dry 15h.3）8h is roasted at 400 DEG C obtains bar shaped sample.4）58.39g nickel nitrate is taken, being made into concentration is 0.7mol/L's
Solution.Step 4 is added in step 3) acquired solution）Impregnate 8h in gained sample, sample filtering is dry, when dry from room temperature with
The heating rate of 15 DEG C/min is slowly raised 140 DEG C, dries 8h at this temperature.5）By sample obtained by step 4) at 400 DEG C
Lower roasting 10h is up to required catalyst.
By 5 catalyst breakage of comparative example at 20-40 mesh, takes 2.0g catalyst loaded in fixed bed reactors, be warming up to 320
Directly charging reaction after DEG C.Reaction pressure 2.0MPa, fuel oil quality air speed are 2.0h-1, H2/ oil volume ratio is 100.React item
Part and the results are shown in Table 2.Comparative example 5 is similar with embodiment 8 catalyst composition, and 8 Sulfur capacity of embodiment is implemented than comparison
Example 5 high 11%.
1 catalyst of table composition
| Embodiment | |
| 1 | 0.18%Ni-1.82%Mo-30%ZnO-50%MnO2-18%Al2O3 |
| 2 | 1.8%Co2O3-18.2%WO3-20%CaO-10%FeO-25%Al2O3-25%SiO2 |
| 3 | 3.5%NiO-2.5%Co2O3-5.0%WO3-20%CaO-10%FeO-20%ZnO-20%Al2O3-10%SiO2-10%SBA15 |
| 4 | 5.0%NiO-2.5%MoO3-2.5%WO3-20%MnO2-10%CaO-50%ZnO-5%Al2O3-5%ZSM5 |
| 5 | 5.0%NiO-2.5%MoO3-2.5%WO3/20%MnO2-10%CaO-45%ZnO-10%FeO/5%Al2O3 |
| 6 | 3.5%NiO-2.0%MoO3-2.5%Co2O3-5.0%WO3/18%CaO-10%FeO-20%ZnO-10%MnO/20%Al2O3-10%SiO2 |
| 7 | 5%NiO-10%WO3/20%ZnO-40%CaO/25%MCM-41 |
| 8 | 7%CO-8%MoO3/40%ZnO-30%CaO/15%SiO2 |
| Comparative example | |
| 1 | 5.0%NiO-20%MnO2-10%CaO-55%ZnO-5%Al2O3-5%ZSM5 |
| 2 | 10.0%NiO/20%MnO2-10%CaO-45%ZnO-10%FeO/5%Al2O3 |
| 3 | 13%NiO/18%CaO-10%FeO-20%ZnO-10%MnO/20%Al2O3-10%SiO2 |
| 4 | 15%NiO/20%ZnO-40%CaO/25%MCM-41 |
| 5 | 15%NiO/40%ZnO-30%CaO/15%SiO2 |
2 reaction condition of table and result
| Embodiment | Temperature, DEG C | Pressure, MPa | Air speed, h-1 | Hydrogen to oil volume ratio, v/v | Desulfurization degree, % | Sulfur capacity, g S/g catalyst |
| 1 | 200 | 0.1 | 0.2 | 10 | 89 | 0.16 |
| 2 | 500 | 5.0 | 5.0 | 600 | 100 | 0.3 |
| 3 | 400 | 3.0 | 4.0 | 300 | 100 | 0.3 |
| 4 | 450 | 10.0 | 3.0 | 200 | 100 | 0.3 |
| 5 | 250 | 7.0 | 2.0 | 100 | 95 | 0.27 |
| 6 | 280 | 2.0 | 2.0 | 100 | 97 | 0.28 |
| 7 | 300 | 2.0 | 2.0 | 100 | 99 | 0.29 |
| 8 | 320 | 2.0 | 2.0 | 100 | 100 | 0.3 |
| Comparative example | ||||||
| 1 | 450 | 10.0 | 3.0 | 200 | 90 | 0.22 |
| 2 | 250 | 7.0 | 2.0 | 100 | 82 | 0.12 |
| 3 | 280 | 2.0 | 2.0 | 100 | 85 | 0.14 |
| 4 | 300 | 2.0 | 2.0 | 100 | 90 | 0.18 |
| 5 | 320 | 2.0 | 2.0 | 100 | 95 | 0.27 |
Claims (11)
1. a kind of coated catalysts, it is characterised in that including hydrodesulfurization activity component, sulfur absorbent and carrier three parts, add
The desulphurizing activated constituent mass score of hydrogen is 2.0-20.0wt%, and sulfur absorbent mass fraction is 30.0-80.0wt%, and surplus is to carry
Body.
2. a kind of coated catalysts as described in claim 1, it is characterised in that the hydrodesulfurization activity component is by AB two
Part forms, A：B molar ratio is 0.1-10, and A is at least one of nickel oxide, cobalt oxide, and B is molybdenum oxide, in tungsten oxide
At least one.
3. a kind of coated catalysts as described in claim 1, it is characterised in that the sulfur absorbent be zinc oxide, manganese oxide,
At least one of iron oxide, calcium oxide.
4. a kind of coated catalysts as described in claim 1, it is characterised in that the carrier is silica, aluminium oxide, molecule
At least one of sieve.
5. a kind of preparation method of coated catalysts according to any one of claims 1-4, it is characterised in that including walking as follows
Suddenly：
(1) sulfur absorbent or its predecessor, carrier or its predecessor and promotor kneading is uniform, extruded moulding；
(2) by sample drying obtained by step (1), 100-150 is increased to from room temperature with the heating rate of 10-20 DEG C/min when dry
DEG C, 6-24h is dried at this temperature；
(3) sample obtained by step (2) is roasted into 3-12h at 400-600 DEG C；
(4) B component predecessor is made into the solution that concentration is 0.05-1mol/L；
(5) step (4) acquired solution is added in sample obtained by step (3) and impregnates 2-20h, sample filtering is dry, when dry
It is increased to 100-150 DEG C from room temperature with the heating rate of 10-20 DEG C/min, dries 6-24h at this temperature；
(6) sample obtained by step (5) is roasted into 3-12h at 400-600 DEG C；
(7) component A predecessor is made into the solution that concentration is 0.05-1mol/L；
(8) step (7) acquired solution is added in sample obtained by step (6) and impregnates 2-20h, sample filtering is dry, when dry
It is increased to 100-150 DEG C from room temperature with the heating rate of 10-20 DEG C/min, dries 6-24h at this temperature；
(9) sample obtained by step (8) is roasted into 3-12h at 400-600 DEG C up to required catalyst.
6. a kind of preparation method of coated catalysts as claimed in claim 5, it is characterised in that step (1) described sulfur absorbent
Predecessor is the hydroxide or carbonate of sulfur absorbent.
7. a kind of preparation method of coated catalysts as claimed in claim 5, it is characterised in that step (1) the carrier forerunner
Object is the hydroxide of carrier.
8. a kind of preparation method of coated catalysts as claimed in claim 5, it is characterised in that step (1) described promotor is
Sesbania powder or soluble starch, additional amount are the 0.5-10wt% of sulfur absorbent.
9. a kind of preparation method of coated catalysts as claimed in claim 5, it is characterised in that before step (4) described B component
Drive the ammonium salt that object is B component.
10. a kind of preparation method of coated catalysts as claimed in claim 5, it is characterised in that step (7) component A predecessor
For the nitrate of component A.
11. a kind of application of coated catalysts according to any one of claims 1-4, it is characterised in that catalyst is used for sulfur-bearing
The desulfurization process of fuel oil, directly charging reaction after reaction temperature is increased to 200-500 DEG C, reaction pressure 0.1-10.0MPa, combustion
Material oil quality air speed is 0.2-5.0h-1, H2/ oil volume ratio is 10-600.
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| CN114433114A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Liquid phase hydrogenation catalyst |
| CN114433058A (en) * | 2020-10-31 | 2022-05-06 | 中国石油化工股份有限公司 | Liquid phase hydrogenation catalyst composition |
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| WO2022089637A1 (en) | 2020-10-31 | 2022-05-05 | 中国石油化工股份有限公司 | Adsorbent, liquid phase hydrogenation catalyst composition, catalyst bed and use thereof |
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