CN109423328A - A kind of method of solvent oil hydrogenation Porous deproteinized bone - Google Patents
A kind of method of solvent oil hydrogenation Porous deproteinized bone Download PDFInfo
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- CN109423328A CN109423328A CN201710733128.2A CN201710733128A CN109423328A CN 109423328 A CN109423328 A CN 109423328A CN 201710733128 A CN201710733128 A CN 201710733128A CN 109423328 A CN109423328 A CN 109423328A
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- Prior art keywords
- catalyst
- reactor
- insulation fix
- fix bed
- bed reactor
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Classifications
-
- 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
- C10G45/44—Hydrogenation of the aromatic hydrocarbons
- C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
- C10G45/48—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
-
- 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
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/18—Solvents
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
A kind of method of solvent oil hydrogenation Porous deproteinized bone, belongs to oil product catalytic refining technical field.By using being used in combination for low Raney nickel and special catalyst loading pattern, under the premise of the not underproduction is not with de- fragrant effect is reduced, control aromatic hydrogenation reaction heat is uniformly released, make the reaction temperature not more than reactor tolerable temperature upper limit, achievees the purpose that safely to carry out hydrogenation dearomatization in the solvent naphtha of 10%-20% to aromatics quality percentage composition in carbon steel insulation fix bed reactor.Method is simple, is easy to industrialize.
Description
Technical field
The invention belongs to oil product catalytic refining technical fields, and in particular to one kind can make aromatics quality percentage composition exist
The method that the solvent naphtha of 10%-20% takes off virtue in carbon steel insulation fix bed reactor.
Background technique
In the production process of solvent oil hydrogenation, according to solvent naphtha type and process conditions, by the solvent naphtha containing aromatic hydrocarbons
120 DEG C -190 DEG C are heated to, by catalyst bed under 0.1MPa-3.0MPa hydro condition, reaches the effect for being saturated aromatic hydrocarbons
Fruit.Usually used is the hydrogenation catalyst that nickel content is 40% or more, and catalyst is filled in hydrogenation dearomatization reactor.Add
Hydrogen takes off arylation reaction device and is designed to carbon steel insulation single tube fixed bed reactors, and the usual reactor use temperature upper limit is 250 DEG C,
The de- virtue of solvent naphtha applied to arene content in raw material less than 10wt%.The temperature rise when solvent oil hydrogenation is not sufficient to exceed carbon steel
Reactor use temperature upper limit.But in process of production, uncertain due to raw material sources, device is changed the line of production production requirement, temporarily
Task dispatching factors need to carry out using solvent naphtha of the existing carbon steel reactor to higher arene content to add hydrogen, as aromatic hydrocarbons contains
The solvent naphtha of 10wt%-20wt% is measured, the solvent naphtha of this higher arene content adds hydrogen in carbon steel single tube fixed bed reactors
When, temperature rise is up to or is more than carbon steel reactor use temperature upper limit, causes de- fragrant device that can not keep the safety in production.
Such issues that common solution be to redesign reactor, single tube adiabatic reactor reactor is changed to tubulation constant temperature
Bed reactor uses heat-resisting reactor material.But this solution lacks for the common de- fragrant device being completed
It economy and takes time and effort；Or temperature rise can be reduced by way of the underproduction, but which increase personnel's consumption of materials, extend
Production time is equally a kind of uneconomic method.
Summary of the invention
The object of the invention: living by reducing per volume of catalyst in reactor under the premise of not changing process units
Property tenor, control reaction speed and response location, reduce de- arylation reaction temperature rise, under the premise of not changing de- fragrant effect,
The higher solvent naphtha of arene content is set safely to carry out hydrogenation dearomatization reaction in carbon steel material insulation fix bed reactor.
Under the premise of not changing structure of reactor, not reducing de- fragrant effect and guarantee yield, control aromatic hydrogenation reaction heat is uniformly put
Out, so that reaction temperature is no more than the reactor tolerable temperature upper limit (250 DEG C), reach in carbon steel insulation fix bed reactor to virtue
Hydrocarbon mass percentage safely carries out hydrogenation dearomatization requirement in 10%-20% solvent naphtha.
Technical solution of the present invention: the method for solvent oil hydrogenation Porous deproteinized bone, it is characterised in that by the solvent naphtha containing aromatic hydrocarbons
It heats, removes the aromatic hydrocarbons in solvent naphtha under hydro condition in the insulation fix bed reactor for being filled with catalyst；The catalysis
Agent segmentation has being seated in insulation fix bed reactor of gradient.
The catalyst segments have being seated in insulation fix bed reactor of gradient, the segmentation filling, and at least two
Section filling exports, volume ratio shared by each section of catalyst from insulation fix bed reactor entrance to insulation fix bed reactor
It successively improves, final stage is 100% pure catalyst.
The catalyst is uniformly mixed with inert particle, and mixed volume ratio is 1:1-1:5.
The inert particle diameter is equal with catalyst granules hydraulic diameter.
The Catalyst packing is two sections of fillings, and 1/2 volume catalyst filling and the uniform of inert particle mix on reactor
Object is closed, 1/2 volume fills 100% catalyst under reactor；The catalyst and inert particle volume ratio are 1:3.
The insulation fix bed reactor is carbon steel insulation fix bed reactor；The catalyst is that Ni-based aromatic hydrogenation is urged
Agent.
The carbon steel insulation fix bed reactor is vertical single tube insulation fix bed reactor, has device for pressure measurement,
There is equally distributed temperature measuring device from top to bottom, temperature measuring point is not more than 1.5 meters/, and use temperature upper limit is 250 DEG C.
Nickel mass percentage in the Ni-based aromatic hydrocarbon hydrogenation catalyst is 20%~22%.
The Ni-based aromatic hydrocarbon hydrogenation catalyst particle is 5 × 5mm of Ф cylindrical.
The solvent naphtha contains boiling range component in 60 DEG C -200 DEG C, and aromatics quality percentage composition is 10%-20%.
Beneficial effects of the present invention:
The present invention can control solvent oil hydrogenation to take off arylation reaction heat and uniformly release, and reach in carbon steel insulation fix bed reactor to virtue
Hydrocarbon mass percentage is that 10%-20% solvent naphtha carries out hydrogenation dearomatization, when taking off constant fragrant effect and the not underproduction, is made anti-
It answers temperature to be no more than 250 DEG C, that is, is no more than carbon steel reactor and uses temperature upper limit safely.
Specific embodiment
Embodiment 1
A: Ф 26mm, which is insulated in single tube reactor, loads Ф 5mm*5mm cylinder nickel system aromatic hydrocarbon hydrogenation catalyst 50mL, catalyst
Middle nickel mass percentage is 40%, bed height 8.6cm.Using thick 120# solvent naphtha as raw material, total virtue content 15.2%.It feeds intake
170 DEG C of temperature, oily air speed 1.0h-1, measurement bed temperature obtains after the 6h that feeds intake, and bed temperature highest point is located at bed inlet
At 0.5cm, 274 DEG C of hot(test)-spot temperature.Always fragrant mass percentage is 0.754% to product.
B: Ф 26mm insulation single tube reactor internal catalyst bed layer lower section filling Ф 5mm × 5mm cylinder nickel system aromatic hydrocarbons adds
Hydrogen catalyst 25mL, nickel mass percentage is 20% in catalyst, lower section bed height 4.3cm.Catalyst bed upper section is again
Load the mixture 25mL, upper section bed height 4.3cm of porcelain ball and catalyst volume ratio 3:1.It is original with thick 120# solvent naphtha
Material, total virtue mass percentage is 15.2%.
170 DEG C of feed temperature, oily air speed 1.0h-1, measurement bed temperature obtains after the 6h that feeds intake, and bed temperature highest point is located at
At bed inlet 4.6cm, 218 DEG C of hot(test)-spot temperature.Always fragrant mass percentage is 0.762% to product.
Embodiment 2
Ningbo oil plant carries out the 120# of arene content 5% or so using the nickel system aromatic hydrocarbon hydrogenation catalyst of Nanjing factory production
Oily hydrogenation dearomatization production, the nickeliferous mass percentage of fresh catalyst are 40%, loaded catalyst 11t.Reactor is general
Logical carbon steel fixed bed adiabatic reactor.Due to factory's buying error, purchases a batch 5000t aromatics quality percentage composition and reach
14.8% raw material.The initial stage factory, which feed intake with 30% load, carries out de- virtue, and 242 DEG C of bed temperature.Enter positioned at catalyst bed
At mouthful.Always fragrant mass percentage is 0.515% to product.
By business accounting, factory plan is produced using low Raney nickel, and factory buying nickel mass percentage is
20% Ф 5mm × 5mm aromatic hydrocarbon hydrogenation catalyst and porcelain ball Ф 5mm porcelain ball, type of feed is using 1/2 volume filling on reactor
The mixture that catalyst is mixed with porcelain sphere volume ratio 1:3,1/2 volume fills 100% catalyst under reactor.
In startup procedure, 160 DEG C of feeding temperature, load is increased to the normal produce load of the factory through 20 hours, bed is most
High-temperature is 221 DEG C, is located in 100% catalyst bed of reactor lower section, in specially 100% catalyst bed at 0.5m.
The total fragrant content 0.530wt% of product.
Embodiment 3
It is mixed with low Raney nickel and different proportion inert ceramic balls, dilution ratio 1:1,1:2,1:3,1:4,1:5 are with embodiment 1
In evaluating apparatus, 1/2 volume is mixture on catalyst bed, and lower 1/2 volume is 100% catalyst.To contain aromatics quality
The 6# solvent naphtha that percentage composition is 20% is that raw material carries out de- virtue, and takes off fragrant Contrast on effect with containing 40% Raney nickel.
* 170 DEG C of feeding temperature, liquid air speed 1.5h-1
Embodiment 4
It is mixed with low Raney nickel and inert ceramic balls 1:3, de- virtue, Catalyst packing is carried out to the 6# solvent naphtha of different arene contents
Mode is the same as b in embodiment 1.
* 170 DEG C of feeding temperature, liquid air speed 1.5h-1
Embodiment 5
It is mixed with low Raney nickel and inert ceramic balls 1:3, de- virtue is carried out to the different boiling range solvent naphthas for being all 15% arene content,
Catalyst loading pattern is the same as b in embodiment 1.
* 170 DEG C of feeding temperature, liquid air speed 1.5h-1。
Claims (10)
1. a kind of method of solvent oil hydrogenation Porous deproteinized bone, it is characterised in that heat the solvent naphtha containing aromatic hydrocarbons, under hydro condition
The aromatic hydrocarbons in solvent naphtha is removed in the insulation fix bed reactor for being filled with catalyst；The catalyst segments have the dress of gradient
It fills out in insulation fix bed reactor.
2. the method as described in claim 1, it is characterised in that: the catalyst segments have being seated in for gradient insulation fix bed
In reactor, the segmentation filling, at least two sections fillings, from insulation fix bed reactor entrance to insulation fix bed reactor
It exports, volume ratio shared by each section of catalyst successively improves, and final stage is 100% pure catalyst.
3. the method as described in claim 1, it is characterised in that the catalyst is uniformly mixed with inert particle, mixed volume
Ratio is 1:1-1:5.
4. method as claimed in claim 3, it is characterised in that: inert particle diameter and catalyst granules hydraulic diameter phase
Deng.
5. the method as described in one of claim 2-4, it is characterised in that: Catalyst packing is two sections and loads, 1/2 on reactor
The homogeneous mixture of volume catalyst filling and inert particle, 1/2 volume fills 100% catalyst under reactor；The catalyst
It is 1:3 with inert particle volume ratio.
6. the method as described in claim 1, it is characterised in that: the insulation fix bed reactor is that carbon steel is insulation fix bed anti-
Answer device；The catalyst is Ni-based aromatic hydrocarbon hydrogenation catalyst.
7. method as claimed in claim 6, it is characterised in that: the carbon steel insulation fix bed reactor is vertical single tube insulation
Fixed bed reactors have device for pressure measurement, have equally distributed temperature measuring device from top to bottom, temperature measuring point is not more than
1.5 meters/, use temperature upper limit are 250 DEG C.
8. method as claimed in claim 6, it is characterised in that: the nickel quality percentage in the Ni-based aromatic hydrocarbon hydrogenation catalyst contains
Amount is 20%~22%.
9. method as claimed in claim 6, it is characterised in that: the Ni-based aromatic hydrocarbon hydrogenation catalyst particle is 5 × 5mm of Ф circle
Cylindricality.
10. the method as described in claim 1, it is characterised in that: the solvent naphtha contains boiling range component in 60 DEG C -200 DEG C, virtue
Hydrocarbon mass percentage is 10%-20%.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201710733128.2A CN109423328A (en) | 2017-08-24 | 2017-08-24 | A kind of method of solvent oil hydrogenation Porous deproteinized bone |
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| CN201710733128.2A CN109423328A (en) | 2017-08-24 | 2017-08-24 | A kind of method of solvent oil hydrogenation Porous deproteinized bone |
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| CN109423328A true CN109423328A (en) | 2019-03-05 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116492935A (en) * | 2023-04-27 | 2023-07-28 | 四川正达凯新材料有限公司 | Hydrogenation catalyst filling method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1393518A (en) * | 2001-07-02 | 2003-01-29 | 中国石油化工股份有限公司 | Grading scheme of hydrocatalyst |
| CN102373065A (en) * | 2010-08-19 | 2012-03-14 | 中国石油化工股份有限公司 | Fixed bed Fischer-Tropsch synthesis method |
| CN103059982A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Heavy oil hydrogenation method |
| CN103666554A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Hydroprocessing method for producing high quality solvent oil |
-
2017
- 2017-08-24 CN CN201710733128.2A patent/CN109423328A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1393518A (en) * | 2001-07-02 | 2003-01-29 | 中国石油化工股份有限公司 | Grading scheme of hydrocatalyst |
| CN102373065A (en) * | 2010-08-19 | 2012-03-14 | 中国石油化工股份有限公司 | Fixed bed Fischer-Tropsch synthesis method |
| CN103059982A (en) * | 2011-10-21 | 2013-04-24 | 中国石油化工股份有限公司 | Heavy oil hydrogenation method |
| CN103666554A (en) * | 2012-09-05 | 2014-03-26 | 中国石油化工股份有限公司 | Hydroprocessing method for producing high quality solvent oil |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116492935A (en) * | 2023-04-27 | 2023-07-28 | 四川正达凯新材料有限公司 | Hydrogenation catalyst filling method |
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Application publication date: 20190305 |