CN105664899A - Method for producing gasoline liquid-phase hydrogenation catalyst carriers - Google Patents
Method for producing gasoline liquid-phase hydrogenation catalyst carriers Download PDFInfo
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- CN105664899A CN105664899A CN201610172766.7A CN201610172766A CN105664899A CN 105664899 A CN105664899 A CN 105664899A CN 201610172766 A CN201610172766 A CN 201610172766A CN 105664899 A CN105664899 A CN 105664899A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 239000007791 liquid phase Substances 0.000 title claims abstract description 25
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 238000005984 hydrogenation reaction Methods 0.000 title abstract description 7
- 239000000969 carrier Substances 0.000 title abstract 4
- 239000000843 powder Substances 0.000 claims abstract description 32
- 239000008188 pellet Substances 0.000 claims abstract description 30
- 239000012498 ultrapure water Substances 0.000 claims abstract description 25
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims abstract description 19
- 238000005406 washing Methods 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000000203 mixture Substances 0.000 claims abstract description 12
- 230000036571 hydration Effects 0.000 claims abstract description 8
- 238000006703 hydration reaction Methods 0.000 claims abstract description 8
- 238000000498 ball milling Methods 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 20
- 239000002994 raw material Substances 0.000 claims description 20
- 229910021502 aluminium hydroxide Inorganic materials 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 229910001593 boehmite Inorganic materials 0.000 claims description 12
- FAHBNUUHRFUEAI-UHFFFAOYSA-M hydroxidooxidoaluminium Chemical compound O[Al]=O FAHBNUUHRFUEAI-UHFFFAOYSA-M 0.000 claims description 12
- 239000011148 porous material Substances 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Natural products CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- 238000001816 cooling Methods 0.000 claims description 10
- 238000005516 engineering process Methods 0.000 claims description 10
- 239000008187 granular material Substances 0.000 claims description 9
- 239000007921 spray Substances 0.000 claims description 9
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 7
- 239000001099 ammonium carbonate Substances 0.000 claims description 7
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 4
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims description 4
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 3
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical compound N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 3
- 239000005695 Ammonium acetate Substances 0.000 claims description 3
- 235000019257 ammonium acetate Nutrition 0.000 claims description 3
- 229940043376 ammonium acetate Drugs 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 238000010298 pulverizing process Methods 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 abstract description 6
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 abstract description 5
- 150000001336 alkenes Chemical class 0.000 abstract description 5
- VXAUWWUXCIMFIM-UHFFFAOYSA-M aluminum;oxygen(2-);hydroxide Chemical compound [OH-].[O-2].[Al+3] VXAUWWUXCIMFIM-UHFFFAOYSA-M 0.000 abstract 1
- 230000002349 favourable effect Effects 0.000 abstract 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 abstract 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 abstract 1
- 238000005507 spraying Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 7
- 238000012216 screening Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 229910052717 sulfur Inorganic materials 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000012141 concentrate Substances 0.000 description 3
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 2
- 229910001948 sodium oxide Inorganic materials 0.000 description 2
- 230000003068 static effect Effects 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
- B01J21/04—Alumina
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
-
- 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
- C10G2300/70—Catalyst aspects
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for producing gasoline liquid-phase hydrogenation catalyst carriers. The method particularly includes 1), smashing aluminum hydroxide and then carrying out flash-roasting on the aluminum hydroxide to prepare raw powder; 2), uniformly mixing the raw powder with pseudo-boehmite with the weight 3-10% of that of the raw powder to obtain mixtures, spraying high-purity water into the mixtures and granulating the mixtures to obtain pellets; 3), carrying out hydration treatment on the pellets and carrying out ball-milling washing and activating on the pellets after the pellets are hardened so as to obtain the aluminum oxide carriers. The method has the advantages that the catalyst carriers produced by the aid of the method are favorable for selective hydrogenation reaction on olefin and mercaptan during gasoline liquid-phase hydrogenation processes.
Description
Technical field
The present invention relates to chemical industry catalysis technical field, be specifically related to the production method of a kind of gasoline liquid phase hydrogenating catalyst carrier.
Background technology
At present, domestic sulfide in petrol content is less than 150ppm, and the U.S. is 30ppm in the world, Europe is 10ppm, domestic content of sulfur in gasoline state of enforcement three standard, sulfur content in gasoline height is considered as air-polluting one of the main reasons, determines to implement in full automobile oil state four standard for this country, sulfur content is reduced to below 50ppm. The key technology reducing sulfur content in gasoline is catalyst technology, and the core of catalyst technology is carrier. There is presently no relevant catalyst carrier technology due to domestic, therefore domestic oil refinery company uses imported catalyst technology.
Summary of the invention
The technical problem to be solved in the present invention is the domestic production method without reference to gasoline liquid phase hydrogenating catalyst carrier, it is provided that the production method of a kind of gasoline liquid phase hydrogenating catalyst carrier.
For solving above-mentioned technical problem, the technical solution used in the present invention is:
A kind of production method of gasoline liquid phase hydrogenating catalyst carrier, method is as follows:
1) with aluminium hydroxide for raw material, after pulverizing, shower roasting prepares former powder;
2) in former powder, add boehmite the mix homogeneously of raw materials quality 3-10%, spray into high purity water and granulate, obtain pellet;
3) gained pellet carries out hydration process, washs through ball milling, activates to obtain alumina support after pellet is hardening.
Further, described shower roasting Temperature Field Control is: inlet temperature 950 ± 20 DEG C, outlet temperature 370 ± 20 DEG C, thermograde 290-310 DEG C/m, material flow 3-5kg/min.
Further, the pore volume of described boehmite is not less than 0.9ml/g.
Further, the washing of described ball milling is: adopt the high purity water of more than 90 DEG C, controls liquid-solid ratio 1:1 and dynamically washs, and the builder of high purity water quality 1-10% is added in the 1st and the 2nd time washing, then high purity water is adopted to wash 3-7 time, the mutual friction of pellet in washing process.
Further, described builder is acetic acid, formic acid, dust technology, ammonium carbonate, ammonium hydrogen carbonate or ammonium acetate.
Further, described calcination for activation Temperature Field Control is: thermograde 240-300 DEG C, preheating zone/m, and zone of constant temperature controls 720 DEG C ± 160 DEG C, cooling band thermograde 220-260 DEG C/m, material flow 0.5-3.0kg/min, kiln speed 0.5-5r/min.
The production method of a kind of gasoline liquid phase hydrogenating catalyst carrier provided by the invention, the alumina support obtained, solve the control technology of the key parameters such as raw material, intensity, purity, pore-size distribution, prepare into gasoline liquid phase hydrogenating catalyst, selectivity of catalyst, activity all reach imported product, product quality is reached advanced world standards, and achieves the production domesticization of gasoline liquid phase hydrogenating catalyst, has promoted the smooth enforcement of state four standard.
Detailed description of the invention
A kind of production method of gasoline liquid phase hydrogenating catalyst carrier, step is as follows:
1) with aluminium hydroxide for raw material, after machinery pulverizing is broken, shower roasting fast dewatering prepares former powder, shower roasting Temperature Field Control is: inlet temperature 930-970 DEG C, outlet temperature 350-390 DEG C, thermograde 290-310 DEG C/m, material flow 3-5kg/min;By the control of sintering temperature field, the former powder ρ-alumina content of preparation reaches more than 80%, and stray crystal content is minimum.
2) in former powder, then add raw materials quality 3-10%, pore volume and be not less than the boehmite additive of 0.9ml/g, mix homogeneously, spray into high purity water and granulate, obtain pellet; The boehmite adding more than pore volume 0.9ml/g just can be effectively improved the bore dia of product, obtains the above macropore content > 5% of product 75nm, pore volume > 0.47ml/g.
3) pellet carries out hydration process, washs, activates, sieves, packs to obtain alumina support product after pellet is hardening.
Described washing process is: adopt the high purity water of more than 90 DEG C, and liquid-solid ratio 1:1 controls dynamically to wash, and the builder of high purity water quality 1-10% is added in the 1st and the 2nd time washing, and then high purity water washs 3-7 time. In washing process, the mutual friction of pellet, grind off the projection on surface, make surface more smooth, also remove the part attachment powder on pellet surface simultaneously, effectively reduce the abrasion of product, abrasion are down within 0.2%. Add builder (acetic acid, formic acid, dust technology, ammonium carbonate, ammonium hydrogen carbonate or ammonium acetate), effectively reduce the sodium oxide content of product, it is down within 0.04%, from bringing other side reactions without product being carried out hydrogenation reaction, and effectively removes the attachment powder of product. Abrasion without the product of washing polishing are about 0.3%, sodium oxide content about about 0.3%.
Activation temperature field controls: thermograde 240-300 DEG C, preheating zone/m, and zone of constant temperature controls 560-880 DEG C, cooling band thermograde 220-260 DEG C/m, material flow 0.5-3.0kg/min, kiln speed 0.5-5r/min. The product obtainedFollowing micropore less than 5%, aperture concentrates onDistribution; The micropore size distribution of the product that prior art produces concentrates onBy controlling activation temperature field, it is stable, moderate that the product of preparation has specific surface area, and pore-size distribution is suitable for the features such as the requirement of gasoline hydrogenation reaction.
Through said process produce gasoline liquid phase hydrogenating catalyst vector product, intensity > 80N/, more than 75nm macropore content > 5%,Following micropore is less than 5%, and aperture concentrates onPore volume > 0.47ml/g, aluminium oxide and hemihydrate content thereof reach more than 99.7%, and specific surface area is 120-220m2/ g, Na2O≤400ppm. Product is conducive to alkene, mercaptan to carry out selective hydrogenation.
Embodiment 1
The present embodiment provides the production method of a kind of gasoline liquid phase hydrogenating catalyst carrier, specific as follows:
With aluminium hydroxide for raw material, it is 12 μm that aluminium hydroxide is crushed to granularity, and shower roasting prepares former powder, and shower roasting inlet temperature is 950 DEG C, outlet temperature is 370 DEG C, thermograde is 300 DEG C/m, material flow is 4kg/min, prepares former powder.
The former powder of gained adds the boehmite that pore volume is 0.9ml/g of raw materials quality 10%, mix homogeneously, sprays into high purity water and granulates, obtains 2-4mm pellet through overmolding.
Pellet hydration process 48h, after hardening, adopt 1.5% dilute nitric acid solution carry out washing twice after, then with high purity water wash 3 times. Then activating, pre-activated torrid zone thermograde is 240 DEG C/m, and it is 650 DEG C that zone of constant temperature controls, and cooling band gradient is 220 DEG C/m, and material flow is 0.5kg/min, and kiln speed is 1r/min, and gained finished product crosses 2-4mm screening, is packaged to be.
The alumina catalyst carrier performance indications obtained are in Table 1, and its activity all reaches, with selecting performance, the prescription that gasoline liquid-phase hydrogenatin is reacted.
Embodiment 2
The present embodiment provides the production method of a kind of gasoline liquid phase hydrogenating catalyst carrier, specific as follows:
With aluminium hydroxide for raw material, it is 9 μm that aluminium hydroxide is crushed to granularity, and shower roasting prepares former powder, and shower roasting inlet temperature is 930 DEG C, outlet temperature is 350 DEG C, thermograde is 300 DEG C/m, material flow is 5kg/min, prepares former powder.
The former powder of gained adds the boehmite that pore volume is 0.97ml/g of raw materials quality 3%, mix homogeneously. Spray into high purity water to granulate, obtain 2-4mm pellet through overmolding.
Pellet hydration process 48h, after hardening, adopt 2.0% dilute acetic acid solution carry out washing twice after, then with high purity water wash 5 times. Then activating, pre-activated torrid zone thermograde is 240 DEG C/m, and it is 670 DEG C that zone of constant temperature controls, and cooling band gradient is 220 DEG C/m, and material flow is 1.5kg/min, and kiln speed is 3r/min, and gained finished product crosses 2-4mm screening, is packaged to be.
The alumina catalyst carrier performance indications obtained are in Table 1, and its activity all reaches, with selecting performance, the prescription that gasoline liquid-phase hydrogenatin is reacted.
Embodiment 3
The present embodiment provides the production method of a kind of gasoline liquid phase hydrogenating catalyst carrier, specific as follows:
With aluminium hydroxide for raw material, it is 13 μm that aluminium hydroxide is crushed to granularity, and shower roasting prepares former powder, and shower roasting inlet temperature is 970 DEG C, outlet temperature is 390 DEG C, thermograde is 300 DEG C/m, material flow is 4.5kg/min, prepares former powder.
The former powder of gained adds the boehmite that pore volume is 0.95ml/g of raw materials quality 7%, mix homogeneously. Spray into high purity water to granulate, obtain 2-4mm pellet through overmolding.
Pellet hydration process 36h, after hardening, adopt 2.5% ammonium bicarbonate soln carry out washing twice after, then with high purity water wash 5 times. Then activating, pre-activated torrid zone thermograde is 300 DEG C/m, and it is 840 DEG C that zone of constant temperature controls, and cooling band gradient is 260 DEG C/m, and material flow is 3.0kg/min, and kiln speed is 5r/min, and gained finished product crosses 2-4mm screening, is packaged to be.
The alumina catalyst carrier performance indications obtained are in Table 1, and its activity all reaches, with selecting performance, the prescription that gasoline liquid-phase hydrogenatin is reacted.
Embodiment 4
The present embodiment provides the production method of a kind of gasoline liquid phase hydrogenating catalyst carrier, specific as follows:
With aluminium hydroxide for raw material, it is 11 μm that aluminium hydroxide is crushed to granularity, and shower roasting prepares former powder, and shower roasting inlet temperature is 960 DEG C, outlet temperature is 380 DEG C, thermograde is 310 DEG C/m, material flow is 4kg/min, prepares former powder.
The former powder of gained adds the boehmite that pore volume is 0.92ml/g of raw materials quality 5%, mix homogeneously. Spray into high purity water to granulate, through being shaped to 2-4mm pellet.
Pellet hydration process 40h, after hardening, adopt 3.0% sal volatile carry out washing twice after, then with high purity water wash 7 times. Then activating, pre-activated torrid zone thermograde is 250 DEG C/m, and it is 800 DEG C that zone of constant temperature controls, and cooling band gradient is 240 DEG C/m, and material flow is 2.0kg/min, and kiln speed is 0.5r/min, and gained finished product crosses 2-4mm screening, packs to obtain product.
The alumina catalyst carrier performance indications obtained are in Table 1, and its activity all reaches, with selecting performance, the prescription that gasoline liquid-phase hydrogenatin is reacted.
Comparative example 1
Comparative example 1 provides the production method of a kind of carrier, specific as follows:
With aluminium hydroxide for raw material, it is 13 μm that aluminium hydroxide is crushed to granularity, and shower roasting prepares former powder, and shower roasting inlet temperature is 900 DEG C, outlet temperature is 350 DEG C, thermograde is 260 DEG C/m, material flow is 5.0kg/min, prepares former powder.
Adopting high purity water to carry out static washing gained pellet, then activate, pre-activated torrid zone thermograde is 300 DEG C/m, it is 700 DEG C that zone of constant temperature controls, and cooling band gradient is 350 DEG C/m, and material flow is 3.0kg/min, kiln speed is 2r/min, and gained finished product crosses 2-4mm screening, is packaged to be.
The alumina catalyst carrier performance indications obtained are in Table 1, and the alkene in gasoline, mercaptan are not had selectivity, it is impossible to for preparing the catalyst of gasoline liquid-phase hydrogenatin reaction.
Comparative example 2
Comparative example 2 provides the production method of a kind of carrier, specific as follows:
With aluminium hydroxide for raw material, it is 11 μm that aluminium hydroxide is crushed to granularity, and shower roasting prepares former powder, and shower roasting inlet temperature is 1030 DEG C, outlet temperature is 450 DEG C, thermograde is 310 DEG C/m, material flow is 4kg/min, prepares former powder.
The former powder of gained adds the boehmite that pore volume is 0.70ml/g of raw materials quality 5%, mix homogeneously. Spray into high purity water to granulate, through being shaped to 2-4mm pellet.
Pellet washs, and adopts vertical stove to activate, and pre-activated torrid zone thermograde is 200 DEG C/m, and it is 450 DEG C that zone of constant temperature controls, and cooling band gradient is 300 DEG C/m, and material flow is 3.0kg/min, and gained finished product crosses 2-4mm screening, packs to obtain product.
The alumina catalyst carrier performance indications obtained are in Table 1, and the alkene in gasoline, mercaptan are not had selectivity, it is impossible to for preparing the catalyst of gasoline liquid-phase hydrogenatin reaction.
Comparative example 3
Comparative example 3 provides the production method of a kind of carrier, specific as follows:
With aluminium hydroxide for raw material, it is 13 μm that aluminium hydroxide is crushed to granularity, and shower roasting prepares former powder, and shower roasting inlet temperature is 950 DEG C, outlet temperature is 350 DEG C, thermograde is 300 DEG C/m, material flow is 5.0kg/min, prepares former powder.
The former powder of gained adds the boehmite that pore volume is 0.80ml/g of raw materials quality 8%, mix homogeneously. Spray into high purity water to granulate, through being shaped to 2-4mm pellet.
High purity water is adopted to carry out static washing gained pellet. Then activating, pre-activated torrid zone thermograde is 300 DEG C/m, and it is 600 DEG C that zone of constant temperature controls, and cooling band gradient is 260 DEG C/m, and material flow is 3.0kg/min, and kiln speed is 2r/min, and gained finished product crosses 2-4mm screening, is packaged to be.
The alumina catalyst carrier performance indications obtained are in Table 1, and the alkene in gasoline, mercaptan are not had selectivity, it is impossible to for preparing the catalyst of gasoline liquid-phase hydrogenatin reaction.
Alumina catalyst carrier performance parameter prepared by table 1 embodiment and comparative example
It should be noted last that, above detailed description of the invention is only in order to illustrate technical scheme and unrestricted, although the present invention being described in detail with reference to example, it will be understood by those within the art that, technical scheme can be modified or equivalent replacement, without deviating from the spirit and scope of technical solution of the present invention, it all should be encompassed in the middle of scope of the presently claimed invention.
Claims (6)
1. the production method of a gasoline liquid phase hydrogenating catalyst carrier, it is characterised in that method is as follows:
1) with aluminium hydroxide for raw material, after pulverizing, shower roasting prepares former powder;
2) in former powder, add boehmite the mix homogeneously of raw materials quality 3-10%, spray into high purity water and granulate, obtain pellet;
3) gained pellet carries out hydration process, washs through ball milling, activates to obtain alumina support after pellet is hardening.
2. production method as claimed in claim 1, it is characterised in that described shower roasting Temperature Field Control is: inlet temperature 950 ± 20 DEG C, outlet temperature 370 ± 20 DEG C, thermograde 290-310 DEG C/m, material flow 3-5kg/min.
3. production method as claimed in claim 1, it is characterised in that the pore volume of described boehmite is not less than 0.9ml/g.
4. production method as claimed in claim 1, it is characterized in that, the washing of described ball milling is: adopt the high purity water of more than 90 DEG C, control liquid-solid ratio 1:1 dynamically to wash, the builder of high purity water quality 1-10% is added in 1st and the 2nd time washing, then high purity water is adopted to wash 3-7 time, the mutual friction of pellet in washing process.
5. production method as claimed in claim 4, it is characterised in that described builder is acetic acid, formic acid, dust technology, ammonium carbonate, ammonium hydrogen carbonate or ammonium acetate.
6. production method as claimed in claim 1, it is characterised in that described calcination for activation Temperature Field Control is: thermograde 240-300 DEG C, preheating zone/m, zone of constant temperature controls 720 DEG C ± 160 DEG C, cooling band thermograde 220-260 DEG C/m, material flow 0.5-3.0kg/min, kiln speed 0.5-5r/min.
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| CN107282028A (en) * | 2017-07-13 | 2017-10-24 | 胡自斌 | It is a kind of to be used for dechlorination, the catalyst of dimethyl ether and preparation method |
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| CN102626618A (en) * | 2012-03-22 | 2012-08-08 | 陕西开达化工有限责任公司 | Palladium alumina catalyst for production of hydrogen peroxide by anthraquinone process and its preparation method |
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| CN101121120A (en) * | 2006-08-11 | 2008-02-13 | 中国石油化工股份有限公司 | Aluminium oxide carrier with composite holes structure and preparation method thereof |
| CN101455959A (en) * | 2008-12-29 | 2009-06-17 | 中国铝业股份有限公司 | Catalyst for regenerating anthraquinone degradation products and preparation method thereof |
| CN102626618A (en) * | 2012-03-22 | 2012-08-08 | 陕西开达化工有限责任公司 | Palladium alumina catalyst for production of hydrogen peroxide by anthraquinone process and its preparation method |
| CN103848451A (en) * | 2012-11-30 | 2014-06-11 | 焦作市华新造纸机械制造有限公司 | Production technology used for preparing activated aluminium oxide balls |
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| CN107282028A (en) * | 2017-07-13 | 2017-10-24 | 胡自斌 | It is a kind of to be used for dechlorination, the catalyst of dimethyl ether and preparation method |
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