CN109988619A - A kind of flexible vaseline hydrogenation technique - Google Patents
A kind of flexible vaseline hydrogenation technique Download PDFInfo
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- CN109988619A CN109988619A CN201711469375.2A CN201711469375A CN109988619A CN 109988619 A CN109988619 A CN 109988619A CN 201711469375 A CN201711469375 A CN 201711469375A CN 109988619 A CN109988619 A CN 109988619A
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- vaseline
- hydroisomerizing
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- hydrogenation
- hydrofinishing
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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
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
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- 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
The invention discloses a kind of flexible vaseline hydrogenation techniques.Vaseline raw material enters hydrofining reactor, is divided into two strands by the material after the Hydrobon catalyst bed of top；One material is extracted out hydrofining reactor among bed, and is entered hydroisomerization reactor and carried out isomerization reaction；Another strand of material continues to flow downwardly through the Hydrobon catalyst bed of lower part；Gained hydrofining reaction material and hydroisomerizing reaction mass carry out gas-liquid separation and fractionation respectively, obtain the vaseline product of different size.The present invention provides for the first time a kind of on a set of hydrogenation technique device while producing the hydrogenation techniques of two or more different size vaseline products, heat entrained by partial hydrogenation purification material can be made full use of, realizes the coupling operation of hydrofining reactor and hydroisomerization reactor.
Description
Technical field
The invention belongs to petroleum refining fields, and in particular to the vaseline that one kind flexibly produces high-quality vaseline product adds hydrogen
Technique.
Background technique
Vaseline is ointment shape oil product with certain characteristics, is important medical, daily-use chemical industry and other are fine
The raw materials for production of chemical products.Vaseline raw material mainly uses residual oil slack wax and lube stock to reconcile, common all scholars
The refining methd of woods has acid-clay-filtered, aluminum chloride treating and hydrofinishing.First two refining methd is due to its product hand rate
It is low, a large amount of reluctant wastes are produced, lead to high production cost, environmental pollution is serious, is gradually hydrogenated purification
Replaced method.
Due to containing more sulphur, nitrogen compound and aromatic hydrocarbons in vaseline raw material, drug and vaseline used for cosmetic are produced
Product need to carry out deep hydrofinishing, and hydrofinishing carries out under severe conditions.Hydrogenation method can effectively remove vaseline raw material
In the heterocycles substance such as sulphur, nitrogen, oxygen, and be saturated condensed-nuclei aromatics.This method three-waste free pollution in process of production, can produce
In high yield, the vaseline product of high quality.CN104910954A, CN001210882A etc. disclose a kind of vaseline and add hydrogen smart
Method processed, can be effectively reduced impurity content, the condensed-nuclei aromatics content of vaseline product, and 103102989 A of CN invention is related to one
The deeply hydrodearomatized method of kind vaseline is processed using noble metal catalyst and using two-stage method process；CN
102453549 A disclose a kind of production method of vaseline, with HVI650 slack wax, reduced pressure distillate oil base oil, selectivity
Decompression residuum slack wax has widened the source of vaseline using hydroisomerization catalyst and Hydrobon catalyst for raw material.
But above-mentioned vaseline hydrogenation technique can only all produce a kind of vaseline product, operating flexibility is poor.
In conclusion vaseline production can be greatly lowered in existing vaseline hydrogen addition technology by the method for hydrofinishing
The impurity contents such as the sulphur nitrogen of product reduce condensed-nuclei aromatics content, improve the property of vaseline product, can also be urged by using isomery
The stringiness that the method for agent increases isomery hydrocarbon content in vaseline product, increases vaseline product, but above-mentioned technology
The vaseline product of production only has one kind, and product flexibility is poor.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of flexible vaseline hydrogenation technique, i.e., by from hydrofinishing
The vaseline raw material is passed through hydrofinishing and hydroisomerizing combined method spirit by extraction section reaction stream in the middle part of reactor
It lives and produces the hydrorefining vaseline product of high quality and with stringiness vaseline product.
A kind of flexible vaseline hydrogenation technique of the invention, includes the following steps:
A, vaseline raw material passes through the Hydrobon catalyst bed on hydrofining reactor top under Hydrofinishing conditions, obtains
To the first hydrotreated refinery stream；This part reaction stream is divided into two parts, and a portion extracts hydrofining reactor out；
B, the first hydrotreated refinery stream continuation of remainder passes through hydrofining reactor under Hydrofinishing conditions in step a
The Hydrobon catalyst bed of lower part, hydrotreated refinery stream are separated, are fractionated to obtain hydrofinishing high pressure hydrogen-rich gas plus hydrogen
Processed gas product, hydrofinishing naphtha product and hydrorefining vaseline product；
C, the first hydrotreated refinery stream of extraction hydrofining reactor obtained by step a is under the conditions of hydroisomerizing by adding hydrogen different
The hydroisomerization catalyst bed of structure reactor, hydroisomerizing logistics separated, be fractionated to obtain hydroisomerizing high pressure hydrogen-rich gas,
Hydroisomerizing gas, hydroisomerizing naphtha and have stringiness vaseline product.
Hydrofining technology according to the present invention, wherein can also include step d: step b obtained hydrofinishing high pressure
It is recycled after the hydroisomerizing high pressure hydrogen-rich gas mixing that hydrogen-rich gas and step c are obtained.
The impurity such as S, N, O in vaseline raw material when the Hydrobon catalyst bed of hydrofining reactor top by obtaining
To effective removing, aromatic hydrocarbons obtains to a certain extent plus hydrogen saturation, a part of reaction stream continue through hydrofining reactor
When the Hydrobon catalyst bed of lower part, hydrogenation reaction depth is deeper, reaches the requirement for producing high-quality vaseline product；Extraction
A part of first hydrotreated refinery stream a part of n-alkane after hydroisomerization catalyst carries out isomerization reaction, is had
There is the vaseline product of stringiness.
Compared with prior art, the advantages of present invention flexible vaseline hydrogenation technique, is:
It 1, include at least two Hydrobon catalyst beds in hydrofining reactor in the present invention.Adding hydrogen by setting
Hydrofinishing material extraction step among finishing reactor bed is not necessarily to special operation, can be realized to hydrofinishing material
Effective distribution of stock, then make obtained material by different hydrogenation techniques, so as to flexibly produce the mesh of different size
Vaseline product.Meanwhile abstraction reaction logistics is technically also to be easily achieved among reactor bed.And existing
In technology, a set of hydrogenation plant is typically only capable to obtain a kind of vaseline product of specification；If it is intended to obtaining all of different size
Intellectual circle's product needs two sets or more of hydrogenation plant.Therefore, the present invention provides one kind on a set of hydrogenation technique device for the first time
The hydroconversion process of two or more different vaseline products is produced simultaneously.
2, the present invention among the catalyst bed of hydrofining reactor by being arranged the extraction of the first hydrotreated refinery stream
Device, the first hydrotreated refinery stream by vaseline raw material Jing Guo hydrofinishing extracts reactor, and is sent to and individually sets
The hydroisomerization reactor set carries out hydroisomerizing reaction, improves the isomery hydrocarbon content of hydroisomerizing vaseline product, so that plus
Hydrogen isomery vaseline has stringiness, so that the vaseline that method of the invention can flexibly produce different isomerization hydrocarbon produces
Product.
3, in the present invention, the vaseline product normal hydrocarbon content obtained after hydrofinishing is high；By partial hydrogenation essence
The vaseline product hydrocarbon isomer content obtained after system, hydroisomerizing is high；The high-quality of the different purpose indexs of production can be met respectively
Vaseline product requirement.
4, in the present invention, the material itself obtained among hydrofining reactor catalyst for refining bed has very high temperature
Degree and pressure, can be directly entered in newly-installed hydroisomerization reactor and be reacted, to make full use of this thigh point
Heat entrained by material is refined, realizes the coupling operation of hydrofining reactor and hydroisomerization reactor.
Detailed description of the invention
Fig. 1 is principle process schematic diagram of the invention.
Wherein: 1- vaseline raw material, 2- hydrofining reactor recycle hydrogen, 3- hydrofining reactor, 4- hydroisomerizing
Feed stream, 5- hydrotreated refinery stream, 6- hydrofinishing high-pressure separator, 7- hydroisomerization reactor, 8- hydroisomerizing logistics,
9- hydroisomerizing high-pressure separator, 10- hydrofinishing stripper or fractionating column, 11- hydroisomerizing stripper or fractionating column, 12-
Hydrofinishing naphtha product, 13- hydrorefining vaseline product, 14- hydroisomerizing naphtha product, 15- hydroisomerizing are all
Intellectual circle's product, 16- hydrofinishing high-pressure separator gaseous product, 17- hydroisomerizing high-pressure separator gaseous product, 18- supplement
Hydrogen.
Specific embodiment
Vaseline feedstock oil described in step a can be single decompression residuum slack wax, can also be with itself and vacuum distillate
The mixture of one or more of tempers of base oil, vacuum distillate dewaxed oil and its solvent-refined oil etc..
Hydrobon catalyst described in step a is conventional catalyst for hydrogenation refining of Vaseline.In hydrogenation catalyst
Hydrogenation active component is one or more of Co, Mo, W, Ni, and the weight content in terms of oxide is 5%~70%；Hydrogenation catalyst
The carrier of agent contains at least one of aluminium oxide, amorphous silicon aluminium, silica, titanium oxide etc., while can help containing other
Agent, such as P, Si, B, Ti, Zr.Commercial catalyst can be used, can also be prepared by this field existing method.Hydrogenation activity group
It is divided into the catalyst of oxidation state, carries out conventional vulcanizing treatment before the use, hydrogenation active component is made to be converted into sulphided state.Quotient
Industry hydrogenation catalyst mainly has, 481-2B, FV-1, FV-10, the FV- developed such as Fushun Petrochemical Research Institute (FRIPP)
20, FV-30 etc..Conventional operating condition, generally reaction pressure 3.0MPa ~ 15.0MPa, volume space velocity can be used in operating condition
For 0.2h-1~6.0h-1, 180 DEG C ~ 400 DEG C of average reaction temperature, hydrogen to oil volume ratio is 100:1~1500:1.
The mass ratio that the fraction of stream of extraction described in step a accounts for feedstock oil in terms of liquid phase is 5~95 wt%, preferably
10~80 wt%.
Separation described in step b generally comprises hydrofinishing high-pressure separator and low pressure separator separates two parts.
The isolated hydrofinishing high pressure hydrogen-rich gas of its high-pressure separator and liquid, the isolated liquid of high-pressure separator enter
Low pressure separator.Low pressure separator is by the isolated hydrocarbon-rich gas of highly pressurised liquid product and low pressure liquid product.Hydrocarbon-rich gas warp
The hydrofinishing gaseous product of isolated needs.
Fractionation described in step b carries out in hydrofinishing stripper or fractionating column system.Low pressure liquid product is in vapour
Fractionation obtains hydrofinishing naphtha product and hydrorefining vaseline product in stripper or fractionating column.
Hydroisomerization catalyst described in step c is conventional vaseline hydroisomerization catalyst, generally with group VIB
And/or group VIII metal is active component, group VIB metal is generally Mo and/or W, group VIII metal be generally Co and/or
Ni.Catalyst carrier contains one of aluminium oxide, silicon-containing alumina and molecular sieve or a variety of, preferably contains molecular sieve, described
Molecular sieve can be for beta molecular sieve, Sapo type molecular sieve etc..With the poidometer of catalyst, group VIB tenor is to aoxidize
Object is calculated as 10wt%~35wt%, and group VIII metal content is calculated as 3wt%~15wt% with oxide, molecular sieve content be 2wt%~
30wt%, alumina content are 10wt%~80wt%.The FC- that main catalyst has Fushun Petrochemical Research Institute to develop
14, FC-20 etc..For catalyst for hydro-upgrading, isomerization reaction occurs for major requirement linear paraffin, and cracking performance wants weak.
Conventional operating condition can be used in the operating condition of hydroisomerizing, generally are as follows: reaction pressure 3.0MPa ~ 15.0MPa, volume space velocity
For 0.2h-1~6.0h-1, 180 DEG C ~ 400 DEG C of average reaction temperature, hydrogen to oil volume ratio is 100:1~1500:1.
The lower part of hydroisomerization reactor described in step c can load supplement Hydrobon catalyst, supplement plus hydrogen essence
Catalyst processed may be the same or different with the Hydrobon catalyst in hydrofining reactor.Hydroisomerizing material is logical
The volume space velocity for crossing supplement Hydrobon catalyst is 1.0h-1~25.0h-1, reaction pressure 3.0MPa ~ 15.0MPa, average response
180 DEG C ~ 400 DEG C of temperature, hydrogen to oil volume ratio is 100:1~1500:1.
Separation described in step c carries out in hydroisomerizing high-pressure separator and low pressure separator.Wherein hydroisomerizing
The isolated hydroisomerizing high pressure hydrogen-rich gas of high-pressure separator and liquid, the isolated liquid of high-pressure separator enter low pressure
Separator.Low pressure separator is by the isolated hydrocarbon-rich gas of highly pressurised liquid product and low pressure liquid product.Hydrocarbon-rich gas is through separating
The hydroisomerizing gaseous product needed.
Fractionation described in step c is stripper or fractionating column system, and low pressure liquid product is in stripper or fractionating column
Fractionation obtains hydroisomerizing naphtha product and hydroisomerizing vaseline product.
Hydrofinishing gas products described in step b and step c and hydroisomerizing gas products can be separately as productions
Product can also be mixed into mixed gas product.
Hydrofinishing naphtha product described in step b and step c and hydroisomerizing naphtha product can individually be made
For product, mixing naphtha product can also be mixed into.
It can be used directly as recycle hydrogen after the mixing of high pressure hydrogen-rich gas described in step d, also can choose and pass through
It is recycled after desulphurization of recycle hydrogen system removing hydrogen sulfide.
In conjunction with Fig. 1, method of the invention is specific as follows: vaseline raw material 1 is mixed into hydrofinishing with recycle hydrogen 2 first
Reactor 3, by extracting hydroisomerizing feed stream 4, extraction plus hydrogen in the reaction stream of the first Hydrobon catalyst bed out
Logistics after isomery feed stream 4 goes successively to follow-up hydrogenation catalyst for refining bed, and hydrofinishing generation logistics 5 enters plus hydrogen
It refines high-pressure separator 6 and carries out gas-liquid separation, isolated liquid enters fractionation in fractionating column 10 and obtains hydrofinishing stone brain
Oil product 12 and hydrorefining vaseline product 14, hydroisomerizing feed stream 4 enters hydroisomerization reactor 7, by adding hydrogen
The generation logistics 8 of heterogeneous catalyst bed, which enters in hydroisomerizing high-pressure separator 9, carries out gas-liquid separation, isolated liquid
Hydroisomerizing naphtha product 14 and hydroisomerizing vaseline product 15, hydrofinishing stone brain are obtained into fractionation in fractionating column 11
Oil product 12 and hydroisomerizing naphtha product 14 can obtain mixing naphtha and produce separately as product after can also mixing
Product, the isolated gas 16 of hydrofinishing high-pressure separator 6 and the isolated gas 17 of hydroisomerizing high-pressure separator 9 are mixed
It is mixed with supplement hydrogen 18 as recycle hydrogen after circulating hydrogen compressor after conjunction.
Illustrate the present invention program and effect below by embodiment.
Embodiment 1-3
Protective agent FZC-100, FZC-105 and FZC106 are China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute
The hydrogenation protecting agent of development and production；Catalyst FV-10 is China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute
The Hydrobon catalyst of development and production；Catalyst FC-20 is that Sinopec Group Fushun petrochemical industry is ground
The hydroisomerization catalyst for studying carefully institute's development and production, contains beta molecular sieve.
1 vaseline raw material main character of table
2 process conditions of table
3 test result of table
It is anti-by extracting a part out out of hydrofining reactor using hydrogenation technique of the invention it can be seen from embodiment
Logistics is answered, and realizes the mesh of production heterogeneity vaseline product using Hydrobon catalyst and hydroisomerization catalyst
, production method is flexible.
Claims (10)
1. a kind of flexible vaseline hydrogenation technique, includes the following steps:
A, vaseline raw material passes through the Hydrobon catalyst bed on hydrofining reactor top under Hydrofinishing conditions, obtains
To the first hydrotreated refinery stream；This part reaction stream is divided into two parts, and a portion extracts hydrofining reactor out；
B, the first hydrotreated refinery stream continuation of remainder passes through hydrofining reactor under Hydrofinishing conditions in step a
The Hydrobon catalyst bed of lower part, hydrotreated refinery stream are separated, are fractionated to obtain hydrofinishing high pressure hydrogen-rich gas plus hydrogen
Processed gas product, hydrofinishing naphtha product and hydrorefining vaseline product；
C, the first hydrotreated refinery stream of extraction hydrofining reactor obtained by step a is under the conditions of hydroisomerizing by adding hydrogen different
The hydroisomerization catalyst bed of structure reactor, hydroisomerizing logistics separated, be fractionated to obtain hydroisomerizing high pressure hydrogen-rich gas,
Hydroisomerizing gas, hydroisomerizing naphtha and have stringiness vaseline product.
2. hydrogenation technique described in accordance with the claim 1, which is characterized in that further include step d: the hydrofinishing that step b is obtained
It is recycled after the hydroisomerizing high pressure hydrogen-rich gas mixing that high pressure hydrogen-rich gas and step c are obtained.
3. hydrogenation technique described in accordance with the claim 1, which is characterized in that it is light that the vaseline feedstock oil is selected from decompression residuum
Dewax cream or decompression residuum slack wax and reduced pressure distillate oil base oil, vacuum distillate dewaxed oil and reduced pressure distillate oil solvent
The mixture of at least one of refined oil.
4. hydrogenation technique described in accordance with the claim 1, which is characterized in that Hydrobon catalyst described in step a with Co,
One or more of Mo, W, Ni be hydrogenation active component, catalyst carrier contain aluminium oxide, amorphous silicon aluminium, silica and
At least one of titanium oxide；With catalyst weight, weight content of the hydrogenation active component in terms of oxide is 5%~70%.
5. hydrogenation technique according to claim 4, the condition of the hydrofinishing are as follows: reaction pressure 3.0MPa ~
15.0MPa, volume space velocity 0.2h-1~6.0h-1, 180 DEG C ~ 400 DEG C of average reaction temperature, hydrogen to oil volume ratio be 100:1~
1500:1。。
6. hydrogenation technique described in accordance with the claim 1, which is characterized in that the logistics extracted out in step a accounts for raw material in terms of liquid phase
The mass ratio of oil is 5~95 wt%, preferably 10~80 wt%.
7. hydrogenation technique described in accordance with the claim 1, which is characterized in that the hydroisomerization catalyst with group VIB and/
Or group VIII metal is active component, catalyst carrier contains one of aluminium oxide, silicon-containing alumina and molecular sieve or a variety of,
The molecular sieve is beta molecular sieve or Sapo type molecular sieve.
8. hydrogenation technique according to claim 7, which is characterized in that with the poidometer of catalyst, group VIB tenor
It is calculated as 10wt%~35wt% with oxide, group VIII metal content is calculated as 3wt%~15wt% with oxide, and molecular sieve content is
2wt%~30wt%, alumina content are 10wt%~80wt%.
9. hydrogenation technique described in accordance with the claim 1, which is characterized in that the condition of the hydroisomerizing are as follows: reaction pressure
3.0MPa ~ 15.0MPa, volume space velocity 0.2h-1~6.0h-1, 180 DEG C ~ 400 DEG C of average reaction temperature, hydrogen to oil volume ratio is
100:1~1500:1.
10. hydrogenation technique according to claim 9, which is characterized in that the lower part of the hydroisomerization reactor, which is loaded, mends
Hydrobon catalyst is filled, hydroisomerizing material is 1.0h by the volume space velocity of supplement Hydrobon catalyst-1~25.0h-1。
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| CN201711469375.2A CN109988619B (en) | 2017-12-29 | 2017-12-29 | Flexible vaseline hydrogenation process |
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|---|---|---|---|
| CN201711469375.2A CN109988619B (en) | 2017-12-29 | 2017-12-29 | Flexible vaseline hydrogenation process |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1611581A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Method for producing soft microcrystalline wax |
| CN1611579A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Method for producing different consistency vaselines |
| CN101492614A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Refining method for vaseline hydrogenation |
| CN103102989A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Method for in-depth hydrogenation and dearomatization of vaseline |
-
2017
- 2017-12-29 CN CN201711469375.2A patent/CN109988619B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1611581A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Method for producing soft microcrystalline wax |
| CN1611579A (en) * | 2003-10-31 | 2005-05-04 | 中国石油化工股份有限公司 | Method for producing different consistency vaselines |
| CN101492614A (en) * | 2008-01-23 | 2009-07-29 | 中国石油化工股份有限公司 | Refining method for vaseline hydrogenation |
| CN103102989A (en) * | 2011-11-10 | 2013-05-15 | 中国石油化工股份有限公司 | Method for in-depth hydrogenation and dearomatization of vaseline |
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Effective date of registration: 20230912 Address after: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee after: CHINA PETROLEUM & CHEMICAL Corp. Patentee after: Sinopec (Dalian) Petrochemical Research Institute Co.,Ltd. Address before: 100728 No. 22 North Main Street, Chaoyang District, Beijing, Chaoyangmen Patentee before: CHINA PETROLEUM & CHEMICAL Corp. Patentee before: DALIAN RESEARCH INSTITUTE OF PETROLEUM AND PETROCHEMICALS, SINOPEC Corp. |