CN109988626A - A kind of flexible two-stage reforming technique - Google Patents
A kind of flexible two-stage reforming technique Download PDFInfo
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- CN109988626A CN109988626A CN201711470923.3A CN201711470923A CN109988626A CN 109988626 A CN109988626 A CN 109988626A CN 201711470923 A CN201711470923 A CN 201711470923A CN 109988626 A CN109988626 A CN 109988626A
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- 238000000034 method Methods 0.000 title claims abstract description 58
- 238000002407 reforming Methods 0.000 title claims abstract description 12
- 238000004517 catalytic hydrocracking Methods 0.000 claims abstract description 101
- 239000003054 catalyst Substances 0.000 claims abstract description 97
- 238000005336 cracking Methods 0.000 claims abstract description 78
- 230000008569 process Effects 0.000 claims abstract description 37
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 239000007791 liquid phase Substances 0.000 claims abstract description 14
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 12
- 239000003921 oil Substances 0.000 claims description 92
- 229910052739 hydrogen Inorganic materials 0.000 claims description 69
- 239000001257 hydrogen Substances 0.000 claims description 69
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 59
- 239000002808 molecular sieve Substances 0.000 claims description 53
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 53
- 239000007789 gas Substances 0.000 claims description 37
- 239000003245 coal Substances 0.000 claims description 30
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 23
- 229910052751 metal Inorganic materials 0.000 claims description 21
- 239000002184 metal Substances 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 16
- 239000002283 diesel fuel Substances 0.000 claims description 12
- 238000000605 extraction Methods 0.000 claims description 7
- 239000003795 chemical substances by application Substances 0.000 claims description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 5
- 230000008859 change Effects 0.000 claims description 5
- 239000010703 silicon Substances 0.000 claims description 5
- 229910052710 silicon Inorganic materials 0.000 claims description 5
- WURBVZBTWMNKQT-UHFFFAOYSA-N 1-(4-chlorophenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)butan-2-one Chemical compound C1=NC=NN1C(C(=O)C(C)(C)C)OC1=CC=C(Cl)C=C1 WURBVZBTWMNKQT-UHFFFAOYSA-N 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 239000000284 extract Substances 0.000 claims description 4
- 241000269350 Anura Species 0.000 claims description 3
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 229910000510 noble metal Inorganic materials 0.000 claims description 3
- 230000009467 reduction Effects 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 239000011280 coal tar Substances 0.000 claims description 2
- 238000004821 distillation Methods 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000003079 shale oil Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 239000010953 base metal Substances 0.000 claims 1
- 238000004140 cleaning Methods 0.000 claims 1
- 230000003647 oxidation Effects 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 15
- 239000007788 liquid Substances 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 9
- 238000000926 separation method Methods 0.000 abstract description 8
- 238000005194 fractionation Methods 0.000 abstract description 6
- 230000008878 coupling Effects 0.000 abstract description 2
- 238000010168 coupling process Methods 0.000 abstract description 2
- 238000005859 coupling reaction Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 136
- 238000005516 engineering process Methods 0.000 description 14
- 239000001993 wax Substances 0.000 description 13
- 238000009833 condensation Methods 0.000 description 10
- 230000005494 condensation Effects 0.000 description 10
- 150000002431 hydrogen Chemical class 0.000 description 10
- 239000004215 Carbon black (E152) Substances 0.000 description 9
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 9
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 8
- 239000012263 liquid product Substances 0.000 description 7
- 238000011160 research Methods 0.000 description 6
- 238000011161 development Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229910052717 sulfur Inorganic materials 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 229910021536 Zeolite Inorganic materials 0.000 description 4
- 239000002199 base oil Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 4
- 238000004230 steam cracking Methods 0.000 description 4
- 239000011593 sulfur Substances 0.000 description 4
- 239000010457 zeolite Substances 0.000 description 4
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 2
- 125000000753 cycloalkyl group Chemical group 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000003223 protective agent Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000000779 smoke Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000013589 supplement Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000011959 amorphous silica alumina Substances 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 230000002101 lytic effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 238000005504 petroleum refining Methods 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 210000000689 upper leg Anatomy 0.000 description 1
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
- 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
-
- 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
- C10G2400/04—Diesel oil
Landscapes
- 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
The invention discloses a kind of flexible two-stage reforming techniques.Wax oil raw material enters separation system after weighted BMO spaces, and gained liquid phase free from foreign meter enters the hydrocracking reactor containing reduction-state hydrocracking catalyst, obtains first and be hydrocracked material being divided into two strands；One material is extracted out hydrocracking reactor among bed, and is reacted into the isocraking reactor containing reduction-state hydroisomerizing Cracking catalyst；Another strand of material continues flow through the hydrocracking catalyst bed of lower part；Gained hydrocracking reaction material and hydroisomerizing cracking reaction material carry out gas-liquid separation and fractionation respectively, obtain the distillate and tail oil product of different size.The present invention provides for the first time a kind of on a set of hydrogenation plant while producing the hydrocracking process of two or more different size distillates and tail oil product, heat entrained by partial cracking material can be made full use of, realizes the coupling operation of hydrocracking reactor and hydroisomerizing cracker.
Description
Technical field
The invention belongs to petroleum refining fields, and in particular to one kind flexibly produces high-quality light naphthar of different nature, again
The two-stage reforming technique of naphtha, boat coal, diesel oil, tail oil product.
Background technique
Hydrogen addition technology is the important manufacturing process of light materialization of heavy oil and light-end products quality upgrading.Hydrocracking technology because
Feedstock oil is adaptable, product flexibility is good, liquid product yield is high, high quality has obtained faster development.
Existing hydrocracking technology can be divided into three kinds according to processing flow: one-stage serial hydrocracking process flow, single hop add hydrogen
Process process and two-stage reforming process flow.According to tail oil, whether circulate operation can be divided into three kinds: one way is primary
Pass through process flow, part circulation technology process and complete alternation process flow.Hydrocracking technology uses two kinds of catalysis
Agent, pretreating catalyst by hydrocracking and hydrocracking catalyst, wherein hydrocracking catalyst is according to using Cracking Component
It is different can be divided into different types of catalyst again, main Cracking Component includes amorphous silica-alumina, Y type molecular sieve, β type point
Son sieve, SAPO Series Molecules sieve and ZSM-5 molecular sieve etc..A group timesharing, obtained light oil are hydrocracked using different type
Product composition and property also have biggish difference, and the composition and property of tail oil also have biggish difference.
A kind of all disclosed method for hydrogen cracking of high-output qulified industrial chemicals of CN103773462A and CN103773463A
Middle gradation uses the two-segment hydrocracking method of two kinds of different Y type molecular sieves.Such technology can pass through using wax oil as feedstock oil
It is yielded products of quality using the method for hydrogen cracking containing Y type molecular sieve hydrocracking catalyst, wherein Determination of Alkane Content in tail oil
Height, BMCI value are low, are the raw material of quality steam cracking ethylene preparation, but are hydrocracked the product of each obtained fraction only
There is a kind of specification.
CN105582992A discloses a kind of hydroisomerisation catalysts and its preparation method and application and a kind of plus hydrogen
Cracking tail oil hydroisomerization process, such technology can using wax oil as feedstock oil, by using contain heterogeneous types molecular sieve
The method for hydrogen cracking of hydrocracking catalyst yields products of quality, and wherein isomery content height, condensation point are low in tail oil, viscosity index (VI)
Height, the product for being the raw material of High Quality Lube Base Oils, but being hydrocracked each obtained fraction only have a kind of specification.
CN103394368B discloses a kind of light oil type hydrogen cracking catalyst and preparation method thereof containing composite molecular screen
And application, CN103551186B disclose a kind of middle oil type hydrocracking catalyst containing composite molecular screen and preparation method thereof and
Using US4837396A discloses a kind of preparation of complex type molecular sieve catalysis.Such technology can using wax oil as feedstock oil,
By using the method for hydrogen cracking containing Y type molecular sieve and heterogeneous types molecular sieve complex type molecular sieve hydrocracking catalyst
Various high-quality hydrocracked products are produced, but the product of each fraction only has a kind of specification.
In conclusion the existing two-stage reforming technology using two kinds of different type molecular sieve catalysts of comparison, makes
With the hydrocracking technology of Y type molecular sieve hydrocracking catalyst, obtained heavy naphtha product sulfur content is low, and virtue is latent opposite
Higher, boat product of coal smoke point is relatively high, and diesel product sulfur content is low, and Cetane number is high, but condensation point is relatively high, and tail oil produces
Product arene content is low, and density is relatively small, and BMCI value is relatively low, but condensation point is very high, and typically larger than 30 DEG C；Use isomery
Types of molecules sieves the hydrocracking technology of hydrocracking catalyst, and obtained heavy naphtha product sulfur content is low, and virtue is latent opposite
Slightly lower, diesel product sulfur content is low, and condensation point is low, but Cetane number is relatively slightly lower, and tail oil density is relatively large, but isohydrocarbon
Content is high, and condensation point is very low, and usually less than 0 DEG C；Using the hydrocracking technology of the complex type molecular sieve catalysis of isomery containing Y-, or
Person's gradation is hydrocracked using hydrocracking catalyst containing Y type molecular sieve and the molecular sieve hydrocracking catalyst containing heterogeneous types
Technology, obtained tail oil property is between using Y type molecular sieve hydrocracking catalyst and use heterogeneous types molecular sieve
Between Cracking catalyst.Above-mentioned hydrocracking process technology, the hydrocracking tail oil product produced in identical conversion ratio are poor
It is not larger, wherein being the quality raw materials of preparing ethylene by steam cracking using the tail oil of Y zeolite catalyst, use heterogeneous types point
The tail oil of sub- sieve catalyst is can directly to produce High Quality Lube Base Oils or the raw material as High Quality Lube Base Oils,
Using hydrocracking catalyst containing Y type molecular sieve and contain isomeric types using the complex type molecular sieve catalysis of isomery containing Y- or gradation
The tail oil that type molecular sieve hydrocracking catalyst obtains can be used as the raw material of preparing ethylene by steam cracking or as high-quality lubrication
The raw material of oil base oil.When above-mentioned several two-stage reforming techniques therefore are used alone, inhomogeneity can only be selected as needed
The hydrocracking catalyst of type, perhaps using two kinds of hydrocracking catalysts of two kinds of molecular sieve composite catalysts or selection
Gradation uses, but these techniques can only produce a kind of tail oil product of property, i.e. operating flexibility compares poor.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provides a kind of flexible two-stage reforming technique, i.e., by from using containing Y
Extraction section reaction stream in the middle part of the hydrocracking reactor of type molecular sieve reduction-state hydrocracking catalyst, by the process
The wax oil feedstock oil of weighted BMO spaces is hydrocracked and reduction-state isomery by the hydrocracking catalyst of reduction-state containing Y type molecular sieve
Type hydrocracking catalyst hydroisomerizing cracking combined method flexibly produces the preparing ethylene by steam cracking raw material, high-quality of high quality
The naphtha product and high-quality automotive fuel product of Lube basic oil material feedstocks and plurality of specifications.
A kind of flexible two-stage reforming technique of the invention, includes the following steps:
A, wax oil feedstock oil enters weighted BMO spaces reactor under the conditions of weighted BMO spaces first and is urged by weighted BMO spaces
Agent bed, obtained weighted BMO spaces logistics isolated high pressure hydrogen-rich gas and liquid phase in high-pressure separator；
B, the weighted BMO spaces liquid phase stream that step a is obtained is anti-by being hydrocracked under hydrocracking condition after imurity-removal
It answers device top to contain the hydrocracking catalyst bed of Y type molecular sieve reduction-state catalyst, obtains first and be hydrocracked logistics, this
Part reaction stream is divided into two parts, and a portion extracts hydrocracking reactor out；
C, in step b the first of remainder be hydrocracked logistics continuation pass through hydrocracking reactor under hydrocracking condition
Lower part contain the hydrocracking catalyst bed of Y type molecular sieve reduction-state catalyst, be hydrocracked logistics and separated, be fractionated
To be hydrocracked high pressure hydrogen-rich gas, be hydrocracked gas product, hydrocracked naphtha product, be hydrocracked boat product of coal,
It is hydrocracked diesel product and hydrocracking tail oil product；
D, first of extraction device obtained by step b is hydrocracked logistics and is split under hydroisomerizing cracking conditions by hydroisomerizing
Change the hydroisomerizing Cracking catalyst bed containing heterogeneous types molecular sieve reduction-state catalyst of reactor, hydroisomerizing cracking
Logistics is separated, is fractionated to obtain hydroisomerizing cracking high pressure hydrogen-rich gas, hydroisomerizing cracked gas product, hydroisomerizing cracking
Naphtha product, hydroisomerizing cracking boat product of coal, hydroisomerizing cracked diesel oil product and hydroisomerizing cracking tail oil product.
Hydrocracking process according to the present invention, wherein can also include step e: the weighted BMO spaces that step a is obtained be high
Hydrogen-rich gas is pressed to use in weighted BMO spaces system circulation；What step c was obtained be hydrocracked high pressure hydrogen-rich gas and step d is obtained
Hydroisomerizing cracking high pressure hydrogen-rich gas mixing after be hydrocracked system circulation use.
The impurity such as S, N, O in wax oil feedstock oil are effectively removed when passing through hydrogenation pretreatment catalyst, and aromatic hydrocarbons is certain
It is obtained in degree plus hydrogen saturation, the weighted BMO spaces liquid phase stream of imurity-removal is continued through containing Y zeolite catalyst
Cyclic hydrocarbon generating unit divides ring-opening reaction when hydrocracking catalyst bed, and aromatic hydrocarbons further adds hydrogen to be saturated, and macromolecular is cracked into small
Molecule, a part are hydrocracked logistics and continue to be hydrocracked, because Y type molecular sieve has the spy of preferential cracking macromolecular cyclic hydrocarbon
Point, available high normal hydrocarbon content, arene content low boat product of coal, diesel product and tail oil product；A part of extraction
First be hydrocracked logistics continue after the hydroisomerizing Cracking catalyst containing heterogeneous types molecular sieve catalyst it is different
Structure is hydrocracked, because heterogeneous types molecular sieve has the characteristics that isomery and cracking, the isomery of available high isomery hydrocarbon content are split
Change product, the condensation point of especially diesel product is low, the condensation point of tail oil product is low, and viscosity index (VI) is high.
Compared with prior art, the advantages of present invention flexible two-stage reforming technique, is:
It 1, include at least two hydrocracking catalyst beds in the hydrocracking reactor of second segment in the present invention.By setting
The cracking material extraction step among hydrocracking reactor bed is set, special operation is not necessarily to, can be realized to being hydrocracked
Effective distribution of material stock, then make obtained material by different hydrocracking process, so as to flexibly produce difference
The purpose product of specification, especially tail oil product.Meanwhile abstraction reaction logistics is technically also easy among reactor bed
In realization.And in the prior art, although the available a variety of lightweights of boiling range by adjusting conversion ratio and adjustment product produce
Product, but since only one hydrocracking reactor exports, a set of same fraction range of hydrocracking unit is usually only
The a type of light naphtha product of energy, heavy naphtha product, boat product of coal and diesel product, especially can only obtain a kind of tail oil
Product；If it is intended to obtaining the hydrocracked product of different size, two sets or more of hydrocracking unit is needed.Therefore, this hair
It is bright to provide one kind for the first time on a set of hydrocracking process device while producing two or more same fraction ranges, but different rule
Lattice tail oil product, two or more different sizes boat product of coal, two or more different size diesel products and a variety of different size stones
The hydrocracking process of naphtha product.
2, the present invention is hydrocracked logistics extraction by the way that first is arranged among the catalyst bed of hydrocracking reactor
Device, by after weighted BMO spaces and imurity-removal liquid phase continue to be hydrocracked first be hydrocracked logistics extract
Reactor out, and be respectively fed to the hydroisomerizing cracker being separately provided and carry out hydroisomerizing cracking reaction, into one
Step reduces this and is hydrocracked the condensation point of rear material, so that method of the invention can flexibly produce different arene contents, no
With the naphtha product of isomery hydrocarbon content, boat product of coal, diesel product and tail oil product.
3, in the present invention, in the product that two reactor streams are fractionated, by adding hydrogen containing Y zeolite catalyst
The heavy naphtha virtue obtained after cracking is dived, and relatively high, boat product of coal smoke point is relatively high, and diesel product Cetane number is relatively
Height, tail oil product paraffinicity is high, BMCI value is relatively low；It is hydrocracked, contains containing Y zeolite catalyst by part
There are the naphtha isomery hydrocarbon content height obtained after heterogeneous types molecular sieve catalyst hydroisomerizing cracking, boat product of coal freezing point low,
Diesel product condensation point is low, and tail oil product hydrocarbon isomer content is high, viscosity index (VI) is big, condensation point is low；The different rule of production can be met respectively
The needs of the naphtha of lattice, navigate product of coal, diesel product and tail oil product.
4, in the present invention, the liquid itself obtained among second segment hydrocracking reactor hydrocracking catalyst bed has
There is very high temperature and pressure, can be directly entered in newly-installed hydroisomerizing cracker and be reacted, to fill
Divide using heat entrained by this thigh division compound material, realizes the coupling of hydroisomerizing cracker and hydrocracking reactor
Closing operation.
Detailed description of the invention
Fig. 1 is principle process schematic diagram of the invention.
Wherein: 1- feedstock oil, 2- weighted BMO spaces reactor, 3- weighted BMO spaces logistics, 4- hydrocracking reactor, 5-
Hydroisomerizing cracked stock logistics, 6- are hydrocracked logistics, 7- hydroisomerizing cracker, and 8- is hydrocracked high pressure separation
Device, 9- hydroisomerizing cracking high-pressure separator, 10- are hydrocracked fractionating column, 11- hydroisomerizing cracking fractionating column, and 12- adds hydrogen to split
Change light naphtha product, 13- is hydrocracked heavy naphtha product, and 14- is hydrocracked boat product of coal, and 15- is hydrocracked diesel oil production
Product, 16- hydrocracking tail oil product, 17- hydroisomerizing cracking light naphtha product, 18- hydroisomerizing cracking heavy naphtha produce
Product, 19- hydroisomerizing cracking boat product of coal, 20- hydroisomerizing cracked diesel oil product, 21- hydroisomerizing cracking tail oil product,
22- is hydrocracked high-pressure separator hydrogen-rich gas, 23- hydroisomerizing cracking high-pressure separator hydrogen-rich gas, 24- weighted BMO spaces
High-pressure separator hydrogen-rich gas, 25- weighted BMO spaces high-pressure separator supplement hydrogen, 26- weighted BMO spaces recycle hydrogen, and 27- adds hydrogen
Cracking recycle hydrogen, the new hydrogen of 28-.
Specific embodiment
The initial boiling point of wax oil raw material described in step a is 100~400 DEG C, and the end point of distillation is 405~650 DEG C.The wax oil is former
Material oil can be one of straight-run gas oil, wax tailings, deasphalted oil, catalytic cycle oil that PETROLEUM PROCESSING obtains etc., from coal
One of obtained coal tar, coal direct liquefaction oil, ICL for Indirect Coal Liquefaction oil, synthetic oil, shale oil etc., be also possible to them its
In several miscella.
Hydrogenation pretreatment catalyst described in step a is conventional wax oil hydrogenation pretreatment catalyst.Generally with VI B race
And/or group VIII metal be active component, using aluminium oxide or silicon-containing alumina as carrier, group VIB metal be generally Mo and/or
W, group VIII metal are generally Co and/or Ni.With the poidometer of catalyst, group VIB tenor is calculated as 10wt% with oxide
~35wt%, group VIII metal content are calculated as 3wt%~15wt% with oxide, and property is as follows: specific surface area be 100~
650m20.15~0.6mL/g of/g, Kong Rongwei.Main catalyst have Fushun Petrochemical Research Institute develop 3936,
3996, FF-16, the hydrogenation pretreatment catalysts such as FF-26, FF-36, FF-46, FF-56 series are also possible to domestic and international catalyst
The function of company's exploitation is similar to catalyst, and such as HC-K, HC-P of Uop Inc., TK-555, TK-565 of Topsoe company are catalyzed
Agent and KF-847, KF-848 of Akzo company etc..Conventional operating condition, generally reaction pressure can be used in operating condition
3.0MPa~19.0MPa, reaction temperature are 300 DEG C~450 DEG C, volume space velocity 0.2h when liquid-1~6.0h-1, hydrogen to oil volume ratio is
100:1~2000:1.
Weighted BMO spaces high-pressure separator described in step a is conventional high-pressure gas-liquid separator.
Weighted BMO spaces liquid phase imurity-removal described in step b can use high pressure stripping, high-pressure washing, high pressure base
The methods of wash, the impurity removals such as the hydrogen sulfide being dissolved in liquid phase, ammonia are fallen.
Hydrocracking catalyst described in step b and step c is conventional wax oil hydrogenation Cracking catalyst.Generally with the VIth
B race and/or group VIII metal are active component, and group VIB metal is generally Mo and/or W, group VIII metal be generally Co and/
Or Ni, it is also possible to one or more of noble metals such as Pt, Pd.The carrier of the catalyst contains aluminium oxide, silicon-containing alumina
With one of molecular sieve or a variety of, preferably contain molecular sieve, the molecular sieve can be Y type molecular sieve.With catalyst
Poidometer, group VIB tenor is calculated as 10wt%~35wt% with oxide, and group VIII metal content is calculated as with oxide
3wt%~15wt%, bullion content are 0.02wt%~2.0wt%, and molecular sieve content is 5wt%~80wt%.Main catalyst
Have that 3824,3825,3976 that Fushun Petrochemical Research Institute develops, FC-12, FC-24, FC-26, FC-32, FC-50 urge
Agent etc., HC-12, HC-14, HC-24, HC-39 etc. of Uop Inc., the HC-18 of Unocal company, HC-28 etc., Chevron
ICR209, ICR211 etc. of company.For hydrocracking catalyst, it is desirable that there is certain hydrogenation activity and certain cracking to live
Property, should guarantee to generate the hydrogen that adds of alkene and aromatic hydrocarbons in fraction in hydrotreating generation oil and hydrocracking process is saturated, and also wants
The reaction of open loop occurs for the aromatic hydrocarbons after seeking saturation.Conventional operating condition can be used in the operating condition being hydrocracked, generally are as follows: anti-
Answer pressure 3.0MPa~19.0MPa, reaction temperature is 150 DEG C~420 DEG C, volume space velocity 0.2h when liquid-1~6.0h-1, hydrogen oil body
Product is than being 100:1~2000:1.
The mass ratio that the fraction of stream of extraction described in step b accounts for feedstock oil in terms of liquid phase is 5~95wt%, preferably
10~80wt%.
Separation described in step c generally comprises be hydrocracked high-pressure separator and low pressure separator separates two parts.
Its high-pressure separator is isolated to be hydrocracked high pressure hydrogen-rich gas and liquid, and the isolated liquid of high-pressure separator enters
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
Isolated needs are hydrocracked gas product.
Fractionation described in step c carries out in being hydrocracked fractionating column system.Low pressure liquid product divides in fractionating column
It evaporates to obtain and is hydrocracked light naphtha product, is hydrocracked heavy naphtha product, is hydrocracked boat product of coal, is hydrocracked diesel oil
Product and hydrocracking tail oil product.
Hydroisomerizing Cracking catalyst described in step d is conventional wax oil hydrogenation isocraking catalyst.Generally with
VI B race and/or group VIII metal are active component, and group VIB metal is generally Mo and/or W；Group VIII metal is generally Co
And/or Ni, it is also possible to one or more of noble metals such as Pt, Pd.The carrier of the catalyst is aluminium oxide, silicon-containing alumina
With it is one or more in molecular sieve, preferably contain molecular sieve, the molecular sieve can be beta molecular sieve, Sapo type molecular sieve
Deng.With the poidometer of catalyst, 10wt%~35wt%, group VIII metal (your non-gold be calculated as with oxide for group VIB tenor
Belong to) content with oxide is calculated as 3wt%~15wt%, bullion content is 0.02wt%~2.0wt%, molecular sieve content be 5wt%~
80wt%.FC-14, FC-20 etc. that main catalyst has Fushun Petrochemical Research Institute to develop, Chevron company
ICR422 etc..For hydrocracking catalyst, it is desirable that have certain hydrogenation activity and certain lytic activity, should guarantee anti-
Answer alkene and aromatic hydrocarbons in material plus hydrogen saturation, also require linear paraffin that isomerization reaction occurs.The operation item of hydroisomerizing cracking
Conventional operating condition can be used in part, generally are as follows: and reaction pressure 3.0MPa~19.0MPa, reaction temperature are 150 DEG C~420 DEG C,
Volume space velocity 0.2h when liquid-1~6.0h-1, hydrogen to oil volume ratio is 100:1~2000:1.
Separation described in step d carries out in hydroisomerizing cracking high-pressure separator and low pressure separator.Wherein plus hydrogen
The isolated hydroisomerizing cracking high pressure hydrogen-rich gas of isocraking high-pressure separator and liquid, high-pressure separator are isolated
Liquid enters low pressure separator.Low pressure separator is by the isolated hydrocarbon-rich gas of highly pressurised liquid product and low pressure liquid product.It is rich
Appropriate hydrocarbon gas is isolated to the hydroisomerizing cracked gas product of needs.
Fractionation described in step d carries out in hydroisomerizing cracking fractionating column system.Low pressure liquid product is in fractionating column
Middle fractionation obtains hydroisomerizing cracking light naphtha product, hydroisomerizing cracking heavy naphtha product, hydroisomerizing cracking boat coal
Product, hydroisomerizing cracked diesel oil product and hydroisomerizing cracking tail oil product.
Gas product and hydroisomerizing cracked gas product are hydrocracked described in step c and step d individually to be made
For product, mixed gas product can also be mixed into.
It is hydrocracked light naphtha product described in step c and step d and hydroisomerizing cracking light naphtha product can
Mixing light naphtha product can also be mixed into separately as product.
It is hydrocracked heavy naphtha product described in step c and step d and hydroisomerizing cracking heavy naphtha product can
Mixing heavy naphtha product can also be mixed into separately as product.
Boat product of coal and hydroisomerizing cracking boat product of coal are hydrocracked described in step c and step d individually to be made
For product, mixing boat product of coal can also be mixed into.
Diesel product and hydroisomerizing cracked diesel oil product are hydrocracked described in step c and step d individually to be made
For product, mixed diesel product can also be mixed into.
Hydrocracking tail oil described in step c is separately as product.
Hydroisomerizing cracking tail oil described in step d is separately as product.
Weighted BMO spaces high pressure hydrogen-rich gas described in step e can be used directly as recycle hydrogen, also can choose
By recycled after desulphurization of recycle hydrogen system removing hydrogen sulfide；Described is hydrocracked high pressure hydrogen-rich gas and hydroisomerizing
It is used after the mixing of cracking high pressure hydrogen-rich gas directly as recycle hydrogen.
Step b, hydrocracking catalyst described in step c and step d and hydroisomerizing Cracking catalyst are before use
It needs to carry out reduction treatment, i.e., carries out the circulate operation of certain time using the hydrogen of heating before catalyst feedstock exposure oil,
The temperature of hydrogen needs to reach 300 DEG C ~ 420 DEG C, and the hydrogen circulate operation time heated at the maximum temperature needs to reach 3 hours
~ 20 hours.
In conjunction with Fig. 1, method of the invention is specific as follows: feedstock oil 1 is mixed into weighted BMO spaces recycle hydrogen 26 first
Weighted BMO spaces reactor 2, weighted BMO spaces logistics 3, which enters in weighted BMO spaces high-pressure separator 25, carries out gas-liquid separation, point
Weighted BMO spaces system circulation is used as after mixing from obtained hydrogen-rich gas 24 after circulating hydrogen compressor is pressurized and with new hydrogen 28
Hydrogen, the isolated liquid phase of weighted BMO spaces high-pressure separator 25 continue after being mixed after imurity-removal with hydrocracking recycle hydrogen 27
It is former by extracting hydroisomerizing cracking in the reaction stream of the first hydrocracking catalyst bed out into hydrocracking reactor 4
Material stream 5, the logistics after extracting hydroisomerizing cracked stock logistics 5 out go successively to follow-up hydrogenation Cracking catalyst bed, add hydrogen
Cracking generates logistics 6 and carries out gas-liquid separation into high-pressure separator 8 is hydrocracked, and isolated liquid enters in fractionating column 10
Fractionation obtains being hydrocracked light naphtha product 12, is hydrocracked heavy naphtha product 14, is hydrocracked boat product of coal 14 plus hydrogen
Cracked diesel oil product 15 and hydrocracking tail oil product 16, hydroisomerizing cracked stock logistics 5 enter hydroisomerizing cracking reaction
Device 7 is entered in hydroisomerizing cracking high-pressure separator 9 by the product stream of hydroisomerizing Cracking catalyst bed and carries out gas-liquid
Separation, isolated liquid enter fractionation in fractionating column 11 and obtain hydroisomerizing cracking light naphtha product 17, hydroisomerizing
Cracking heavy naphtha product 18, hydroisomerizing cracking boat product of coal 19, hydroisomerizing cracked diesel oil product 20 and hydroisomerizing are split
Change tail oil product 21, is hydrocracked light naphtha product 12 and hydroisomerizing cracking light naphtha product 17 can be separately as production
Product obtain mixing light naphtha product, are hydrocracked heavy naphtha product 13 and hydroisomerizing cracking scheelite after can also mixing
Naphtha product 18 can obtain mixing heavy naphtha product, be hydrocracked boat product of coal separately as product after can also mixing
14 and hydroisomerizing cracking boat product of coal 19 can separately as product, be obtained after can also mixing mixing boat product of coal, add hydrogen
Cracked diesel oil product 15 and hydroisomerizing cracked diesel oil product 20 can obtain mixing bavin separately as product after can also mixing
Oil product, is hydrocracked the isolated gas 22 of high-pressure separator 8 and hydroisomerizing cracking high-pressure separator 9 is isolated
Gas 23 mixes to be used as after circulating hydrogen compressor is pressurized after mixing with supplement hydrogen 28 is hydrocracked system circulation hydrogen.
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 FF-56 is China Petroleum and Chemical Corporation Fushun Petrochemical Research Institute
The hydrotreating catalyst of development and production；Catalyst FC-32 is that Sinopec Group Fushun petrochemical industry is ground
The catalyst for hydro-upgrading for studying carefully institute's development and production, contains Y type molecular sieve；Catalyst FC-20 is that Sinopec's share is limited
The hydroisomerizing Cracking catalyst of Fushun Petrochemical Research Institute, company development and production, contains beta molecular sieve.
The main character of 1 wax oil feedstock oil of table
2 embodiment process conditions of table
2 process conditions of continued
3 test result of table
Using flexible two-stage reforming technique of the invention it can be seen from embodiment, by out of hydrocracking reactor
It extracts a part of reaction stream out, and is realized using reduction-state hydrocracking catalyst and reduction-state hydroisomerizing Cracking catalyst
The purpose of heterogeneity hydrocracked product is produced, production method is flexible.
Claims (18)
1. a kind of flexible two-stage reforming technique, includes the following steps:
A, wax oil feedstock oil enters weighted BMO spaces reactor under the conditions of weighted BMO spaces first and is urged by weighted BMO spaces
Agent bed, obtained weighted BMO spaces logistics isolated high pressure hydrogen-rich gas and liquid phase in high-pressure separator；
B, the weighted BMO spaces liquid phase stream that step a is obtained is anti-by being hydrocracked under hydrocracking condition after imurity-removal
It answers device top to contain the hydrocracking catalyst bed of Y type molecular sieve reduction-state catalyst, obtains first and be hydrocracked logistics, this
Part reaction stream is divided into two parts, and a portion extracts hydrocracking reactor out；
C, in step b the first of remainder be hydrocracked logistics continuation pass through hydrocracking reactor under hydrocracking condition
Lower part contain the hydrocracking catalyst bed of Y type molecular sieve reduction-state catalyst, be hydrocracked logistics and separated, be fractionated
To be hydrocracked high pressure hydrogen-rich gas, be hydrocracked gas product, hydrocracked naphtha product, be hydrocracked boat product of coal,
It is hydrocracked diesel product and hydrocracking tail oil product；
D, first of extraction device obtained by step b is hydrocracked logistics and is split under hydroisomerizing cracking conditions by hydroisomerizing
Change the hydroisomerizing Cracking catalyst bed containing heterogeneous types molecular sieve reduction-state catalyst of reactor, hydroisomerizing cracking
Logistics is separated, is fractionated to obtain hydroisomerizing cracking high pressure hydrogen-rich gas, hydroisomerizing cracked gas product, hydroisomerizing cracking
Naphtha product, hydroisomerizing cracking boat product of coal, hydroisomerizing cracked diesel oil product and hydroisomerizing cracking tail oil product.
2. hydrocracking process described in accordance with the claim 1, which is characterized in that further include step e: step a is obtained plus hydrogen
High pressure hydrogen-rich gas is pre-processed to use in weighted BMO spaces system circulation；What step c was obtained be hydrocracked high pressure hydrogen-rich gas and
System circulation use is being hydrocracked after the hydroisomerizing cracking high pressure hydrogen-rich gas mixing that step d is obtained.
3. hydrocracking process described in accordance with the claim 1, which is characterized in that the initial boiling point of the wax oil feedstock oil is 100
~400 DEG C, the end point of distillation is 405~650 DEG C.
4. hydrocracking process described in accordance with the claim 3, which is characterized in that the wax oil feedstock oil is selected from straight run wax
Oil, wax tailings, deasphalted oil, coal tar, coal direct liquefaction oil, ICL for Indirect Coal Liquefaction oil, synthetic oil, shale oil and catalytic cycle
At least one of oil.
5. hydrocracking process described in accordance with the claim 1, which is characterized in that hydrogenation pretreatment catalyst described in step a
Using VI B race and/or group VIII metal as active component, using aluminium oxide or silicon-containing alumina as carrier；With the poidometer of catalyst,
Group VIB tenor is calculated as 10wt%~35wt% with oxide, group VIII metal content with oxide be calculated as 3wt%~
15wt%；Its property is as follows: specific surface area is 100~650m20.15~0.6mL/g of/g, Kong Rongwei.
6. hydrocracking process described in accordance with the claim 1, which is characterized in that the operating condition of the weighted BMO spaces are as follows:
Reaction pressure 3.0MPa~19.0MPa, reaction temperature are 300 DEG C~450 DEG C, volume space velocity 0.2h when liquid-1~6.0h-1, hydrogen oil
Volume ratio is 100:1~2000:1.
7. hydrocracking process described in accordance with the claim 1, which is characterized in that weighted BMO spaces liquid phase described in step b
Imurity-removal is fallen the hydrogen sulfide being dissolved in liquid phase, ammonia impurity removal using high pressure stripping, high-pressure washing or high pressure alkali cleaning.
8. hydrocracking process described in accordance with the claim 1, which is characterized in that be hydrocracked and urge described in step b and step c
For agent using group VIB and/or group VIII metal as active component, the carrier of the catalyst contains aluminium oxide and/or siliceous oxidation
Aluminium and molecular sieve, the molecular sieve are Y type molecular sieve.
9. hydrocracking process according to claim 8, which is characterized in that with the poidometer of catalyst, group VIB metal
Content is calculated as 10wt%~35wt% with oxide, and group VIII metal content is calculated as 3wt%~15wt%, molecular sieve content with oxide
For 5wt%~80wt%.
10. hydrocracking process according to claim 8, which is characterized in that the hydrocracking catalyst is with noble metal
Pt and/or Pd is active component, and bullion content is calculated as 0.02wt%~2.0wt% with oxide.
11. hydrocracking process described in accordance with the claim 1, which is characterized in that the hydrocracking condition are as follows: reaction pressure
Power 3.0MPa~19.0MPa, reaction temperature are 150 DEG C~420 DEG C, volume space velocity 0.2h when liquid-1~6.0h-1, hydrogen to oil volume ratio
For 100:1~2000:1.
12. hydrocracking process described in accordance with the claim 1, which is characterized in that the logistics extracted out in step b is accounted in terms of liquid phase
The mass ratio of feedstock oil is 5~95wt%, preferably 10~80wt%.
13. hydrocracking process described in accordance with the claim 1, which is characterized in that the hydroisomerizing Cracking catalyst with
Group VIB and/or group VIII metal are active component, and group VIB metal is Mo and/or W, and group VIII metal is Co and/or Ni,
Or group VIII metal is selected from Pt and/or Pd；Catalyst carrier contains in aluminium oxide and/or silicon-containing alumina and molecular sieve, institute
Stating molecular sieve is beta molecular sieve or Sapo type molecular sieve etc..
14. hydrocracking process according to claim 13, which is characterized in that with the poidometer of catalyst, group VIB gold
Belong to content and 10wt%~35wt% is calculated as with oxide, the VIIIth race's base metal content is calculated as 3wt%~15wt% with oxide, molecule
Sieve content is 5wt%~80wt%.
15. hydrocracking process according to claim 13, which is characterized in that with the poidometer of catalyst, Pt and/or Pd
Content is calculated as 0.02wt%~2.0wt% with oxide.
16. hydrocracking process described in accordance with the claim 1, which is characterized in that the condition of the hydroisomerizing cracking are as follows: anti-
Answer pressure 3.0MPa~19.0MPa, reaction temperature is 150 DEG C~420 DEG C, volume space velocity 0.2h when liquid-1~6.0h-1, hydrogen oil body
Product is than being 100:1~2000:1.
17. hydrocracking process described in accordance with the claim 1, which is characterized in that the hydrocracking catalyst and plus hydrogen
Isocraking catalyst is using preceding carry out reduction treatment.
18. hydrocracking process according to claim 17, which is characterized in that the process of the reduction treatment are as follows: use
The hydrogen of heating carries out circulate operation, and the temperature of hydrogen is 300 DEG C ~ 420 DEG C, at the maximum temperature the hydrogen circulate operation time be
3 ~ 20 hours.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1415707A (en) * | 2001-10-30 | 2003-05-07 | 中国石油化工股份有限公司 | Method for increasing prodn. of good quality diesel oil from distillation cut oil |
| CN101003749A (en) * | 2006-12-31 | 2007-07-25 | 厦门大学 | Method for starting operation of catalyst for hydrocracking in oxidation state |
| CN101942333A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Shale oil single-stage serial hydrocracking technology method |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1415707A (en) * | 2001-10-30 | 2003-05-07 | 中国石油化工股份有限公司 | Method for increasing prodn. of good quality diesel oil from distillation cut oil |
| CN101003749A (en) * | 2006-12-31 | 2007-07-25 | 厦门大学 | Method for starting operation of catalyst for hydrocracking in oxidation state |
| CN101942333A (en) * | 2009-07-09 | 2011-01-12 | 中国石油化工股份有限公司抚顺石油化工研究院 | Shale oil single-stage serial hydrocracking technology method |
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