CN106281463A - A kind of hydrorefining paraffin wax technique - Google Patents
A kind of hydrorefining paraffin wax technique Download PDFInfo
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- CN106281463A CN106281463A CN201610671750.0A CN201610671750A CN106281463A CN 106281463 A CN106281463 A CN 106281463A CN 201610671750 A CN201610671750 A CN 201610671750A CN 106281463 A CN106281463 A CN 106281463A
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- paraffin
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- 239000012188 paraffin wax Substances 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000001257 hydrogen Substances 0.000 claims abstract description 23
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 23
- 239000003054 catalyst Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000001993 wax Substances 0.000 claims abstract description 16
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 15
- -1 tungsten nitride Chemical class 0.000 claims abstract description 12
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 claims abstract description 11
- 229910039444 MoC Inorganic materials 0.000 claims abstract description 11
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 11
- 239000010937 tungsten Substances 0.000 claims abstract description 11
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 claims abstract description 11
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 10
- 239000011733 molybdenum Substances 0.000 claims abstract description 10
- 150000002431 hydrogen Chemical class 0.000 claims abstract description 8
- 229910003178 Mo2C Inorganic materials 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 5
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 5
- 210000000988 bone and bone Anatomy 0.000 claims abstract description 3
- 238000010348 incorporation Methods 0.000 claims abstract description 3
- 238000005516 engineering process Methods 0.000 claims description 10
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 26
- 239000011593 sulfur Substances 0.000 abstract description 26
- 229910052717 sulfur Inorganic materials 0.000 abstract description 26
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 13
- 241000269350 Anura Species 0.000 abstract description 3
- 238000006477 desulfuration reaction Methods 0.000 abstract description 3
- 230000023556 desulfurization Effects 0.000 abstract 1
- 230000000694 effects Effects 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 239000010779 crude oil Substances 0.000 description 9
- 239000012467 final product Substances 0.000 description 9
- 239000002808 molecular sieve Substances 0.000 description 9
- 239000003921 oil Substances 0.000 description 9
- 235000019198 oils Nutrition 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 9
- 235000016768 molybdenum Nutrition 0.000 description 8
- 238000007670 refining Methods 0.000 description 8
- 239000002994 raw material Substances 0.000 description 7
- 230000002079 cooperative effect Effects 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- URRHWTYOQNLUKY-UHFFFAOYSA-N [AlH3].[P] Chemical compound [AlH3].[P] URRHWTYOQNLUKY-UHFFFAOYSA-N 0.000 description 3
- 238000013459 approach Methods 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 238000004517 catalytic hydrocracking Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- IVSZLXZYQVIEFR-UHFFFAOYSA-N m-xylene Chemical group CC1=CC=CC(C)=C1 IVSZLXZYQVIEFR-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910002796 Si–Al Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000007233 catalytic pyrolysis Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000008157 edible vegetable oil Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000004992 fission Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000006317 isomerization reaction Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910003158 γ-Al2O3 Inorganic materials 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
- C10G73/00—Recovery or refining of mineral waxes, e.g. montan wax
- C10G73/42—Refining of petroleum waxes
- C10G73/44—Refining of petroleum waxes in the presence of hydrogen or hydrogen-generating compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/82—Phosphates
- B01J29/84—Aluminophosphates containing other elements, e.g. metals, boron
- B01J29/85—Silicoaluminophosphates [SAPO compounds]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/183—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself in framework positions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a kind of hydrorefining paraffin wax technique, described technique uses fixed bed reactors, is filled with hydrogenation desulfurization and denitrogenation catalyst in fixed bed reactors, and described catalyst includes carrier and active component；Described carrier is incorporation hetero atom Cu in synthetic bone shelf structure2+SAPO 5；Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc；The reaction condition of described fixed bed reactors is: reaction temperature is 250 300 DEG C, and hydrogen dividing potential drop is 2.8 3.6MPa, hydrogen wax volume ratio 150 300, volume space velocity 0.6 2.0h‑1.Paraffin total sulfur content can be controlled, less than 5ppm, to control the total nitrogen content in paraffin within 10ppm by this technique simultaneously.
Description
Technical field
The present invention relates to wax hydrofining desulfuration purification technique, be specifically related to a kind of paraffin using special catalyst to carry out and add
Hydrogen process for refining.
Background technology
Paraffin is the one of refinery products, is through solvent refining, solvent from the lube cut of crude distillation gained
Dewaxing or prepare slack wax through wax freezing and crystallizing, squeezing dewaxing, then through solvent deoiling, refined obtained by lamellar or acicular crystal.
Paraffin is divided into the big class such as food wax, paraffin wax fully refined, semi-refined paraffin wax, waxy stone, match wax and black wax.Paraffin is divided into
Many grades are sold, and the main distinction is that fusing point is different.According to the difference of purposes, different to the prescription of paraffin.Due to from
The waxy stone of oil contains numerous impurity such as sulfur, and therefore it can not use directly as product, needs through process for refining, to protect
Holding the deep refining realizing product while the characteristic index such as the fusing point of product, oil content, needle penetration are basically unchanged, refined is deep
Degree should meet following requirement: is 1. hydrogenated with by the non-hydrocarbons of sulfur, nitrogen, oxygen, removes sulfur therein, nitrogen and oxygen；2. by alkene,
Aromatic hydrocarbons particularly condensed-nuclei aromatics hydrogenation is saturated；3. reduce the cracking reaction occurring C-C bond fission to generate little molecule, it is to avoid add as far as possible
Hydrogen oil content in paraffin wax increases.
And in numerous paraffin process for refining, hydrorefining paraffin wax technique can keep feedstock skeleton knot due to it
In the case of structure does not changes or varies less, by impurity removal, reach to change the purpose that oil product has been eaten, therefore obtain wide
General application.By the end of 2005, the designed capacity of the hydrorefining paraffin wax process units of the domestic normal operation of China was close
1.3Mt/a, wherein single covering device maximum processing capacity is 150kt/a.
Along with heaviness, the in poor quality of world's crude oil are deepened day by day, crude oil sulfur content is more and more higher, and the lightweight of high-quality is former
Oil is constantly reducing.The crude oil of refinery's processing in recent years mostly is imported crude oil, and relative density increases year by year, in several years of the beginning of this century
The average density of whole world refinery processing crude oil rises to about 0.8633.The problem that sulfur content is high is the most extremely serious, the current world
The yield of upper sour crude oil and sour crude accounts for more than the 75% of world's crude oil total output.20th century the mid-90 whole world refinery
The crude oil average sulfur content of processing is 0.9%, and the beginning of this century has increased to 1.6%.
Current hydrorefining paraffin wax technique, similar with fraction oil hydrogenation refining, generally comprise pretreatment of raw material, hydrogenation instead
Answer and product post processing three parts.Paraffin typically through pretreatment such as filtration, degassings, the impurity that carries in removing raw material,
The gaseous oxygen etc. of minor amount of water, solvent and dissolving, then mix with hydrogen, heat entrance reactor, carry out hydrofining reaction.Reaction
Product carries out gas-liquid separation respectively in high pressure and low pressure separator, then through stripping, being dried and be filtrated to get finished product wax.
But existing hydrorefining paraffin wax technique is all to arrange for former high-quality edible vegetable oil.For current high-sulfur
The paraffin that content crude oil production obtains, owing to its high sulfur content, its catalyst used and hydroconversion condition are all difficult to be suitable for.
The most how paraffin process for refining is provided, can effectively the sulfur content in the starting paraffin of high sulfur content be controlled
Below 10ppm, to meet standard, is a difficult problem facing of this area.
Summary of the invention
It is an object of the invention to propose a kind of wax hydrofining desulfuration purification technique, this technique can be by the total sulfur in paraffin
Content is reduced to below 10ppm, with satisfied discharge and Corrosion standards.
For reaching this purpose, the present invention by the following technical solutions:
A kind of hydrorefining paraffin wax technique, described technique uses fixed bed reactors, is filled with and adds in fixed bed reactors
Hydrogen catalyst, described catalyst includes carrier and active component.
Described carrier is incorporation hetero atom Cu in synthetic bone shelf structure2+SAPO-5.
Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc.
The reaction condition of described fixed bed reactors is: reaction temperature is 250-300 DEG C, and hydrogen dividing potential drop is 2.8-3.6MPa,
Hydrogen wax volume ratio 150-300, volume space velocity 0.6-2.0h-1。
SAPO-5 molecular sieve is the one in SAPO (SAPO) Series Molecules sieve, and its channel system is by six sides couple
The twelve-ring that the four-membered ring of title property and hexatomic ring are constituted is constituted, and has large aperture structure, and its aperture is 0.8nm.SAPO-5
Acidic zeolite is gentle, and has faint controllability, also has cation exchange capacity (CEC).In a way, its materialization
Character not only has the characteristic of aluminophosphate molecular sieve, and also is similar to the characteristic of Si-Al zeolite.Owing to it has novel
Crystal structure, good heat stability and hydrothermal stability, in meta-xylene isomerization and normal hexane catalytic pyrolysis etc. react
Tool is widely used.But it is used for hydrofinishing rather than hydrocracking field, rarely seen document is reported.
The present invention through in numerous silicoaluminophosphamolecular molecular sieves, such as SAPO-11, SAPO-17, SAPO-20, SAPO-31,
SAPO-34, SAPO-44, SAPO-46, SAPO-47 etc., carry out contrast test selection one by one, finds that only SAPO-5 can reach
The goal of the invention of the present invention, other mesoporous materials have such-and-such defect, exist when being applied in the present invention and are difficult to gram
The technical difficulty of clothes, therefore the present invention selects to turn the SAPO-5 modification being used for being hydrocracked to do for hydrorefined carrier base
Plinth.
Inventor finds through research, for affecting the silica alumina ratio of silicoaluminophosphamolecular molecular sieves performance, phosphorus aluminum ratio, in the present invention
In, after being modified, the change of silica alumina ratio and phosphorus aluminum ratio is less to hydrofinishing influential effect, and therefore the present invention is no longer to sial
It is defined than with phosphorus aluminum ratio.For ease of the explanation present invention, typically it is defined to mol ratio and is respectively less than 1.
Owing to existing SAPO-5 molecular sieve catalytic temperature is high, and being easily caused raw material hydrocracking, therefore, the present invention is to it
Being modified, to increase its catalysis activity, reduce catalytic temperature and make it be applicable to catalytic refining, minimizing is hydrocracked.This
The bright approach to the modification of SAPO-5 mesopore molecular sieve is: introduce to the total silicon SAPO-5 mesopore molecular sieve duct inner surface of finished product
Cu2+, this approach can be exchanged Cu by ion2+It is supported on the inner surface of SAPO-5, thus improves on the whole
Catalysis activity, absorption and the Thermodynamically stable performance etc. of SAPO-5 mesopore molecular sieve.
Although the method being modified SAPO-5 mesopore molecular sieve or approach are a lot, inventor finds, the present invention urges
Agent can only use doping Cu2+SAPO-5 could realize sulfur content as carrier and control and the balance of loss of octane number, invention
People has attempted adulterating in SAPO-5: Ca2+、Fe3+、Zn2+、Ti2+、Ga3+And alkali metal etc. produces anionic surface center
Ion, finds all to realize described effect.Although described mechanism is current and unclear, but this has no effect on the reality of the present invention
Executing, inventor is according to well-known theory and it is experimentally confirmed that there is cooperative effect between itself and the active component of the present invention.
Described Cu2+Doping in SAPO-5 must control within specific content range, and its doping is with weight
Meter, for the 0.56%-0.75% of SAPO-5 weight, such as 0.57%, 0.58%, 0.59%, 0.6%, 0.61%, 0.62%,
0.63%, 0.64%, 0.65%, 0.66%, 0.67%, 0.68%, 0.69%, 0.7%, 0.71%, 0.72%, 0.73%,
0.74 etc..
Inventor finds, outside this range, can cause drastically reducing of paraffin desulfurized effect.It is more pleasurable,
Work as Cu2+When doping in SAPO-5 controls in the range of 0.63%-0.72%, its desulphurizing ability is the strongest, when drawing with Cu2 +Doping is transverse axis, and during curve chart with target desulfurized effect as the longitudinal axis, in this content range, sulfur content can control extremely low
Within the scope of, its desulfurized effect produced, far beyond expection, belongs to unforeseeable technique effect.
The total content of described active component is the 1%-15% of carrier S APO-5 weight, preferably 3-12%, further preferably
5-10%.Such as, described content can be 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%,
7%, 7.5%, 8%, 8.5%, 9%, 9.5%, 10%, 10.5%, 11%, 11.5%, 12%, 12.5%, 13%,
13.5%, 14%, 14.5% etc..
In the present invention, it is particularly limited to active component for nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Mixed proportion, inventor find, the effect that different mixed proportions reaches is entirely different.Inventor finds, nitrogenizes two molybdenums
MO2N, tungsten nitride W2N, molybdenum carbide Mo2The mixed proportion (mol ratio) of C and tungsten carbide wc is 1:(0.4-0.6): (0.28-
0.45): (0.8-1.2), nitridation two molybdenum MO are only controlled2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc exists
In the range of Gai, sulfur content in paraffin can be realized and control at below 10ppm and denitrification ability notable.It is to say, the present invention
Four kinds of active components be only 1:(0.4-0.6 in mol ratio): (0.28-0.45): time (0.8-1.2), just possess collaborative effect
Should.Outside this molar ratio range, or omit or replace any one component, all can not realize cooperative effect.
Preferably, two molybdenum MO are nitrogenized2N, tungsten nitride W2N, molybdenum carbide Mo2The mol ratio of C and tungsten carbide wc is 1:(0.45-
0.5): (0.35-0.45): (0.8-1.0), more preferably 1:(0.45-0.48): (0.4-0.45): (0.9-1.0),
Preferably 1:0.48:0.42:0.95.
The preparation method of described catalyst can take infusion process and other alternative methods, the people in the art of routine
The prior art unrestricted choice that member can grasp according to it, the present invention repeats no more.
Preferably, the reaction condition of described fixed bed reactors is: reaction temperature is 260-280 DEG C, and hydrogen dividing potential drop is 2.8-
3.0MPa, hydrogen wax volume ratio 150-200, volume space velocity 1.0-1.5h-1。
Preferably, described technological process includes, raw material, after filter, surge tank, is pumped into heat exchanger by feed pump and become
Product heat exchange, is mixed to form hydrogen wax mixture, again enters heating furnace with after product heat exchange with recycle hydrogen and new hydrogen after heat exchange,
Being heated to reaction temperature and enter hydrofining reactor (fixed bed reactors), hydrogen wax mixture is made at catalyst in the reactor
Under with, the reaction such as carry out that hydrodesulfurization, denitrogenation, deoxidation, alkene is saturated and aromatic hydrocarbons is saturated, product is through heat exchange more water cooled
To predetermined temperature, entering high-pressure separator, high-pressure separator top gas phase returns recycle hydrogen surge tank as recycle hydrogen, and oil phase enters
Entering low pressure separator, the generation oil drawn bottom low pressure separator enters stripper, tower top oil gas warp after product heat exchange
Entering separatory tank after air cooling, water-cooled and obtain Petroleum, stripping tower bottom obtains paraffin.
Preferably, described fixed bed reactors include 1-5 beds, further preferred 2-3 beds.
The hydrofining technology of the present invention is by choosing specific catalyst, and described catalyst is by mixing hetero atom Cu2+
SAPO-5 as carrier, and choose the nitridation two molybdenum MO of special ratios2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
As active component so that this catalyst produces cooperative effect, and the hydrodesulfurization to paraffin can control to be less than at total sulfur content
5ppm, controls within 10ppm the total nitrogen content in paraffin simultaneously.
Detailed description of the invention
The hydrofining technology of the present invention is illustrated by the present invention by following embodiment.
Embodiment 1
Preparing catalyst by infusion process, carrier is doping Cu2+SAPO-5, Cu2+Doping in SAPO-5
Control at the 0.65% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Total content is carrier quality 10%, its mol ratio is 1:0.4:0.3:0.8.
Described Catalyst packing enters fixed bed reactors, and the reaction tube of described reactor is by the stainless steel of internal diameter 50mm
Becoming, beds is set to 3 layers, and reaction bed temperature UGU808 type temp controlled meter is measured, and raw material paraffin is by Bei Jingwei
The double plunger micro pump of star maker manufacture carries continuously, and hydrogen is supplied and use Beijing Sevenstar-HC D07-11A/ by gas cylinder
ZM mass-flow gas meter coutroi velocity, loaded catalyst is 2kg.Reacted product cools down laggard circulation of qi promoting through water-bath room temperature
Liquid separates.
Raw materials used for paraffin, its total sulfur content 561ppm, basic n content is 258ppm.
Controlling reaction condition is: temperature 270 DEG C, hydrogen dividing potential drop 3.0MPa, hydrogen wax volume ratio 200, volume space velocity 1.5h-1。
Testing final product, total sulfur content is reduced to 3ppm, and total alkaline nitrogen content is reduced to 12ppm.
Embodiment 2
Preparing catalyst by infusion process, carrier is doping Cu2+SAPO-5, Cu2+Doping in SAPO-5
Control at the 0.7% of carrier quality.Described active component nitrogenizes two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and tungsten carbide wc
Total content is carrier quality 10%, its mol ratio is 1:0.6:0.45): 1.2.
Remaining condition is same as in Example 1.
Testing final product, total sulfur content is reduced to 4ppm, and total alkaline nitrogen content is reduced to 10ppm.
Comparative example 1
The carrier of embodiment 1 is replaced with γ-Al2O3, remaining condition is constant.
Testing final product, total sulfur content is reduced to 34ppm, and total alkaline nitrogen content is reduced to 42ppm.
Comparative example 2
The carrier of embodiment 1 is replaced with unadulterated SAPO-5, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 31ppm, and total alkaline nitrogen content is reduced to 40ppm.
Comparative example 3
Cu by embodiment 12+Replace with Zn2+, remaining condition is constant.
Testing final product, total sulfur content is reduced to 35ppm, and total alkaline nitrogen content is reduced to 55ppm.
Comparative example 4
By the Cu in embodiment 12+Doping in SAPO-5 controls at the 0.5% of carrier quality, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 33ppm, and total alkaline nitrogen content is reduced to 48ppm.
Comparative example 5
By the Cu in embodiment 12+Doping in SAPO-5 controls at the 0.8% of carrier quality, and remaining condition is constant.
Testing final product, total sulfur content is reduced to 26ppm, and total alkaline nitrogen content is reduced to 52ppm.
Embodiment 1 shows with comparative example 1-5, certain content scope that the application uses and certain loads metal ion
SAPO-5 carrier, when replacing with other known carriers of this area, or carrier is identical but Cu2+During doping difference, all reach
Less than the technique effect of the present invention, the therefore Cu of the certain content scope of the present invention2+Doping SAPO-5 carrier and catalyst other
Possessing cooperative effect between component, described hydrofining technology creates unforeseeable technique effect.
Comparative example 6
Omit the MO in embodiment 12N, remaining condition is constant.
Testing final product, total sulfur content is reduced to 46ppm, and total alkaline nitrogen content is reduced to 61ppm.
Comparative example 7
Omitting the WC in embodiment 1, remaining condition is constant.
Testing final product, total sulfur content is reduced to 42ppm, and total alkaline nitrogen content is reduced to 58ppm.
Above-described embodiment and comparative example 6-7 explanation, several active component of catalyst of the hydrofining technology of the present invention it
Between there is specific contact, be omitted or substituted one of which or several, all can not reach the certain effects of the application, it was demonstrated that it produces
Give birth to cooperative effect.
Applicant states, the present invention illustrates the technique of the present invention by above-described embodiment, but the invention is not limited in
Above-mentioned technique, does not i.e. mean that the present invention has to rely on above-mentioned detailed catalysts and could implement.Those of skill in the art
Member is it will be clearly understood that any improvement in the present invention, and the equivalence of raw material each to product of the present invention is replaced and the interpolation of auxiliary element, tool
Body way choice etc., within the scope of all falling within protection scope of the present invention and disclosure.
Claims (6)
1. a hydrorefining paraffin wax technique, described technique uses fixed bed reactors, is filled with hydrogenation in fixed bed reactors
Catalyst, described catalyst includes carrier and active component, it is characterised in that
Described carrier is incorporation hetero atom Cu in synthetic bone shelf structure2+SAPO-5,
Described active component is nitridation two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide Mo2C and the mixture of tungsten carbide wc,
The reaction condition of described fixed bed reactors is: reaction temperature is 250-300 DEG C, and hydrogen dividing potential drop is 2.8-3.6MPa, hydrogen wax
Volume ratio 150-300, volume space velocity 0.6-2.0h-1。
2. hydrofining technology as claimed in claim 1, it is characterised in that hetero atom Cu2+Doping be SAPO-5 weight
0.63%-0.72%.
3. hydrofining technology as claimed in claim 1, it is characterised in that the total content of described active component is carrier
The 3-12% of SAPO-5 weight, preferably 5-10%.
4. hydrofining technology as claimed in claim 1, it is characterised in that nitrogenize two molybdenum MO2N, tungsten nitride W2N, molybdenum carbide
Mo2The mol ratio of C and tungsten carbide wc is 1:(0.45-0.5): (0.35-0.45): (0.8-1.0), more preferably 1:
(0.45-0.48): (0.4-0.45): (0.9-1.0), most preferably 1:0.48:0.42:0.95.
5. hydrofining technology as claimed in claim 1, it is characterised in that the reaction condition of described fixed bed reactors is:
Reaction temperature is that reaction temperature is 260-280 DEG C, and hydrogen dividing potential drop is 2.8-3.0MPa, hydrogen wax volume ratio 150-200, volume space velocity
1.0-1.5h-1。
6. hydrofining technology as claimed in claim 1, it is characterised in that described fixed bed reactors include 1-5 catalysis
Agent bed, preferably includes 2-3 beds.
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