CN1891792A - Petroleum solvent oil refining adsorbent, and its preparing method and use - Google Patents
Petroleum solvent oil refining adsorbent, and its preparing method and use Download PDFInfo
- Publication number
- CN1891792A CN1891792A CN 200510114239 CN200510114239A CN1891792A CN 1891792 A CN1891792 A CN 1891792A CN 200510114239 CN200510114239 CN 200510114239 CN 200510114239 A CN200510114239 A CN 200510114239A CN 1891792 A CN1891792 A CN 1891792A
- Authority
- CN
- China
- Prior art keywords
- petroleum spirit
- molecular sieve
- preparation
- hours
- type molecular
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses the treating adsorbent of the petroleum spirit and its preparation method and use. The preparation method of the treating adsorbent includes the following steps: dipping X type molecular sieve in nitrate solution; washing it by de-ionized water; drying it at 80-150 centigrade degree for 1-10 hours; and roasting it at 300-700 centigrade degree for 2-10 hours. The treating adsorbent can be used to refine 6# and 120# petroleum spirit at normal temperature. And its processing technology is simple; and the effect of alkene and arene casting is obvious.
Description
Technical field
The present invention relates to treating adsorbent of a kind of petroleum spirit and its production and use.This sorbent material is suitable for 6# and 120# petroleum spirit, and to carry out deolefination, aromatic hydrocarbons etc. at normal temperatures refining.
Background technology
Petroleum spirit is to be used for some material is played the oils that dissolving, dilution, washing and extracting etc. act on.The whole world is annual to consume about 2,000 ten thousand tons of all kinds of petroleum spirits, and wherein the petroleum-type petroleum spirit accounts for wherein half.Before the eighties in 20th century, petroleum-type series petroleum spirit of less types, change of properties is also little.But enter the later stage eighties 20th century, because the environmental requirement increasingly stringent, the consideration of petroleum spirit user of service's health and safety more and more is subject to people's attention.
The main raw material of petroleum series petroleum spirit production has three sources, and the one, crude oil straight run, the 2nd, catalytic reforming is raffinated oil, and the 3rd, condensate oil.They normally are made of one group of close hydrocarbon molecule of boiling point, can express with boiling spread so describe them.Initial boiling point temperature, final boiling point (or doing) temperature as petroleum spirit are exactly two important parameters of petroleum spirit, and the boiling range scope is narrow more, and then quality product is good more.Alkene in the petroleum spirit and aromaticity content are the leading indicators of weighing the petroleum solvent oil quality, also are the gap places of present homemade raw petroleum solvent oil and external high-grade petroleum spirit.Production with the normal hexane solvent is example, and its raw material has straight run gas oil and oil field gas condensate oil, aromatic extraction unit petroleum cuts such as raffinate oil.Domestic enterprise generally adopts aromatic hydrocarbons to raffinate oil to be the raw material processing, utilize this raw material characteristics of sulfur-bearing (sulphur content is less than 1 μ g/g) hardly, be processed into the normal hexane solvent through hydrofining, but alkene wherein and aromaticity content and external expensive goods differ bigger.
Petroleum spirit takes off the aromatic hydrocarbons technology at present four kinds: hydrogenation method, adsorption method of separation, sulfonation method and extraction fractional distillation.
Petroleum spirit hydrogenation aromatics-removing method at home and abroad is most widely used, and particularly raffinating oil with catalytic reforming is the raw material production petroleum spirit, and is convenient because of hydrogen source, how to make with extra care with hydrogenation method.Some have the refinery of hydrogen source also to make with extra care with straight-run spirit with hydrogenation method is the petroleum spirit of raw material production.The aromatic hydrocarbons technology of taking off of Daqing Petroleum Institute's exploitation, can make aromaticity content in the 6# petroleum spirit drop to 500 μ g/g (Wang Guangwei, Li Fengrong, Tang Jixin etc. high aromaticity content 6# extracting petroleum spirit shortening takes off aromatic hydrocarbons. Daqing Petroleum Institute's journal, 1997,21 (3): 32-36).Hydrogenation method be difficult to make in the petroleum spirit aromaticity content particularly heavy aromatics obviously reduce, and only be applicable to the occasion of sufficient hydrogen source.
Publication number is that 1243114 Chinese patent discloses a kind of hydrocarbon adsorption dearylating hydrocarbon technology, can be that 40～300 ℃, aromaticity content are that 0.1%～15% hydrocarbon material flow is after fractionation by adsorption with boiling range, aromaticity content drops to below the 100 μ g/g, and the sorbent used balance aromatic hydrocarbons adsorptive capacity of this technology is up to 25%.
Publication number is that 1112154 Chinese patent has been set forth a kind of petroleum solvent sulfoxidation purification techniques, can make the aromaticity content in the petroleum spirit drop to 200-1000 μ g/g.Be difficult to effective utilization but the shortcoming of sulfonation method is an acid sludge, the particularly high aromaticity content petroleum spirit loss of not only acid sludge difficult treatment, and petroleum spirit is too big.
Extraction fractional distillation is only limited to No. 6 (6#) petroleum spirits at present and takes off aromatic hydrocarbons.This method is to be extraction agent with the N-Methyl pyrrolidone, and the method by extracting rectifying removes the benzene in the petroleum spirit No. 6, can make its benzene content drop to 0.2%～0.5% (Liu Chengjun. oil and gas chemical industry .1999,28 (2): 86-88).
The alkene that removes in the petroleum spirit mainly contains absorption method and two kinds of methods of hydrogenation hydride process at present.Generally speaking, absorption method can be carried out desorption by carclazyte, and granular carclazyte is to be processed through chemical treatment by natural bentonite ore.It is widely used in removing alkene and boat matchmaker's decolorizing and refining in petrochemical complex, this mainly is to utilize its surface to have more weak solid acid and bigger adsorption surface area.The active size of granular carclazyte also depends primarily on the total amount and the active adsorption surface-area at surperficial weak acid center, thereby makes the olefin catalytic in the oil product aggregate into polymer, removes by absorption again.The basic nitrogen compound of boat in the coal then adsorbed by surperficial solid acid, thus also reach the decolorizing and refining purpose (Wang Hong. boat jet system technological transformation. the Hebei chemical industry, 2003,5:38-40).
Another method that removes the alkene of aromatic hydrocarbons in raffinating oil is to pass through shortening, this also can reduce alkene and aromaticity content greatly, again through the boiling range cutting, can get corresponding high-quality petroleum spirit (the HEY JUDE pearl. reformed oil and the hydrogenation and olefin hydrocarbon removal of raffinating oil are produced the new technology of petroleum spirit. the Speciality Petrochemicals progress, 2000,1 (7): 32-35).But catalytic hydrogenation reaction generally needs medium-pressure or high pressure, at least also wants the pressure of several MPa, and all than higher, this just brings certain difficulty to workman's operation, is difficult to be widely used in the middle of the operation of actual factory to the requirement of the requirement of equipment and catalyzer.
Obviously, making with extra care of impurity such as existing petroleum solvent oil-off olefin, aromatic hydrocarbons is little for industrial scale, alkene and aromaticity content require harsh high-grade petroleum spirit production to have certain technology and cost problem, must seek the process for purification of impurity such as new deolefination, aromatic hydrocarbons.
Summary of the invention
One of purpose of the present invention provides a kind of petroleum spirit treating adsorbent, and it can be used in 6# and the 120# petroleum spirit carries out the refining of impurity such as deolefination, aromatic hydrocarbons at normal temperatures.
Another object of the present invention provides a kind of preparation method of described petroleum spirit treating adsorbent.This method is that metal oxide is loaded on the X type molecular sieve by pickling process, obtains this sorbent material through washing, dry, roasting.This preparation method's step is:
1) with nitrate solution dipping X type molecular sieve;
2) the X type molecular sieve deionized water wash after will flooding;
3) the X type molecular sieve after will washing 80～150 ℃ dry 1～10 hour down;
4) with dried X type molecular sieve 300～700 ℃ of following roastings 2～10 hours, obtain described sorbent material.
Wherein, the preferred normal temperature of the dipping temperature of step 1), preferred 7 days of dipping time; Step 2) is the nitrate that is not attached on the X type molecular sieve in order to remove; Step 3) is in order to remove the free-water on the X type molecular sieve behind the load nitrate; The nitrate of load obtains corresponding metal oxide on the molecular sieve in order to decompose in the roasting of step 4).
The preferred IA-IIA of nitrate solution wherein, VIII, the nitrate solution of IB-IIB family metallic element is as KNO
3, AgNO
3, Mg (NO
3)
2, Co (NO
3)
2, Ni (NO
3)
2, Cu (NO
3)
2, Zn (NO
3)
2, especially preferred Cu (NO
3)
2And Zn (NO
3)
2Solution.
The preferred 2-20 of mass ratio of nitrate and X type molecular sieve in the nitrate solution wherein: 100, described preferred 10X of X type molecular sieve or 13X molecular sieve.
Wherein the drying temperature in the step 3) is preferred 110 ℃, preferred 2 hours of time of drying.
Wherein the maturing temperature in the step 4) is preferred 500 ℃, preferred 5 hours of roasting time.
According to the petroleum spirit treating adsorbent that preparation method of the present invention obtains, its advantage is: be applicable to that 6# and 120# petroleum spirit carry out the refining of impurity such as deolefination, aromatic hydrocarbons at normal temperatures, treatment process is simple, deolefination and to take off the aromatic hydrocarbons effect obvious.
Embodiment
Further describe a kind of petroleum spirit treating adsorbent of the present invention and preparation method thereof below by specific embodiment.
Embodiment 1
Use Ni (NO
3)
2Solution impregnation 10X type molecular sieve, Ni (NO
3)
2The mass ratio ratio of solid and molecular sieve is 5: 100, the mixture that obtains behind the dipping with deionized water wash after, 80 ℃ of dryings 3 hours, then 400 ℃ of roastings 4 hours.
Embodiment 2
Use Ni (NO
3)
2Solution impregnation 10X type molecular sieve, Ni (NO
3)
2The mass ratio ratio of solid and molecular sieve is 10: 100, the mixture that obtains behind the dipping with deionized water wash after, 80 ℃ of dryings 3 hours, then 400 ℃ of roastings 4 hours.
Embodiment 3
Use Ni (NO
3)
2Solution impregnation 10X type molecular sieve, Ni (NO
3)
2The mass ratio ratio of solid and molecular sieve is 10: 100, the mixture that obtains behind the dipping with deionized water wash after, 100 ℃ of dryings 3 hours, then 400 ℃ of roastings 4 hours.
Embodiment 4
Use Ni (NO
3)
2Solution impregnation 10X type molecular sieve, Ni (NO
3)
2The mass ratio ratio of solid and molecular sieve is 10: 100, the mixture that obtains behind the dipping with deionized water wash after, 100 ℃ of dryings 3 hours, then 500 ℃ of roastings 4 hours.
Embodiment 5
Use Zn (NO
3)
2Solution impregnation 10X type molecular sieve, Zn (NO
3)
2The mass ratio ratio of solid and molecular sieve is 5: 100, the mixture that obtains behind the dipping with deionized water wash after, 80 ℃ of dryings 3 hours, then 400 ℃ of roastings 4 hours.
Embodiment 6
Use Zn (NO
3)
2Solution impregnation 10X type molecular sieve, Zn (NO
3)
2The mass ratio ratio of solid and molecular sieve is 10: 100, the mixture that obtains behind the dipping with deionized water wash after, 80 ℃ of dryings 3 hours, then 400 ℃ of roastings 4 hours.
Embodiment 7
Use Zn (NO
3)
2Solution impregnation 10X type molecular sieve, Zn (NO
3)
2The mass ratio ratio of solid and molecular sieve is 10: 100, the mixture that obtains behind the dipping with deionized water wash after, 100 ℃ of dryings 3 hours, then 400 ℃ of roastings 4 hours.
Embodiment 8
Use Zn (NO
3)
2Solution impregnation 10X type molecular sieve, Zn (NO
3)
2The mass ratio ratio of solid and molecular sieve is 10: 100, the mixture that obtains behind the dipping with deionized water wash after, 100 ℃ of dryings 3 hours, then 500 ℃ of roastings 4 hours.
Embodiment 9
Use Ni (NO
3)
2Solution impregnation 13X type molecular sieve, Ni (NO
3)
2The mass ratio ratio of solid and molecular sieve is 5: 100, the mixture that obtains behind the dipping with deionized water wash after, 80 ℃ of dryings 3 hours, then 400 ℃ of roastings 4 hours.
Embodiment 10
Use Ni (NO
3)
2Solution impregnation 13X type molecular sieve, Ni (NO
3)
2The mass ratio ratio of solid and molecular sieve is 10: 100, the mixture that obtains behind the dipping with deionized water wash after, 80 ℃ of dryings 3 hours, then 400 ℃ of roastings 4 hours.
Embodiment 11
Use Ni (NO
3)
2Solution impregnation 13X type molecular sieve, Ni (NO
3)
2The mass ratio ratio of solid and molecular sieve is 10: 100, the mixture that obtains behind the dipping with deionized water wash after, 100 ℃ of dryings 3 hours, then 400 ℃ of roastings 4 hours.
Embodiment 12
Use Ni (NO
3)
2Solution impregnation 13X type molecular sieve, Ni (NO
3)
2The mass ratio ratio of solid and molecular sieve is 10: 100, the mixture that obtains behind the dipping with deionized water wash after, 100 ℃ of dryings 3 hours, then 500 ℃ of roastings 4 hours.
Embodiment 13
Present embodiment obtains the effect experiment of sorbent material for embodiment 1.
Adopt micro-doubleplunger pump that pending petroleum spirit is fed from continuous adsorption treatment unit bottom, through the adsorbent of molecular sieve layer for preparing in advance in the device, when the first dropstone Oil solvent oil flows out from continuous adsorption treatment unit top, as zero timing point, later every through getting one time sample in one hour.The molecular sieve filling volume is 150ml, and air speed is 0.5-1.5h
-1, the aromaticity content that sample is flowed out in experiment adopts liquid chromatographic detection, and olefin(e) centent adopts JF-3 type bromine valency, bromine index determinator to detect.Experimental result: 6# petroleum spirit aromaticity content 2.1% before not removing, bromine index 2624,120# petroleum spirit aromaticity content 2.24%, bromine index 1589, utilize molecular sieve can successfully remove alkene in 6# and the 120# petroleum spirit, for the 6# petroleum spirit, bromine index can drop to below 400; For the 120# petroleum spirit, bromine index can drop to below 300, simultaneously the arene engaging scraping rate in the petroleum spirit is reached more than 90%, and aromatic hydrocarbons is dropped to below 0.2%.Detailed results sees Table 1.
Table 1 6# and bromine index and the aromaticity content of 120# petroleum spirit in the different elution times
| Time (hr) | 0 | 2 | 4 | 6 | 8 | 10 | 12 | On average |
| The bromine index of 120# | 0.12 | 0.22 | 0.33 | 0.59 | 65.59 | 780.6 | 1099 | 278.06 |
| The aromaticity content of 120# (m%) | 0.02 | 0.07 | 0.22 | 0.38 | 0.52 | 0.92 | 1.32 | 0.493 |
| The bromine index of 6# | 0.32 | 0.43 | 2.56 | 20.87 | 98.87 | 980 | 1265 | 338.29 |
| The aromaticity content of 6# (m%) | 0.01 | 0.05 | 0.14 | 0.32 | 0.45 | 0.76 | 0.95 | 0.383 |
It should be noted last that: above embodiment is the unrestricted technical scheme of the present invention in order to explanation only, although the present invention is had been described in detail with reference to the foregoing description, those of ordinary skill in the art is to be understood that, still can make amendment and/or be equal to replacement, and not break away from the spirit and scope of the present invention the present invention.
Claims (10)
1, a kind of preparation method of petroleum spirit treating adsorbent the steps include:
1) with nitrate solution dipping X type molecular sieve;
2) the X type molecular sieve deionized water wash after will flooding;
3) the X type molecular sieve after will washing 80～150 ℃ dry 1～10 hour down;
4) with dried X type molecular sieve 300～700 ℃ of following roastings 2～10 hours, obtain described sorbent material.
2, according to the preparation method of the described petroleum spirit treating adsorbent of claim 1, wherein, the nitrate solution described in the step 1) is IA-II A, VIII, the nitrate solution of IB-II B family metallic element.
3, according to the preparation method of the described petroleum spirit treating adsorbent of claim 2, wherein, described nitrate solution is Cu (NO
3)
2Or Zn (NO
3)
2
4, according to the preparation method of the described petroleum spirit treating adsorbent of claim 1, wherein, the dipping temperature of step 1) is a normal temperature, and dipping time is 7 days.
5, according to the preparation method of the described petroleum spirit treating adsorbent of claim 1, wherein, the mass ratio of nitrate described in the step 1) in the nitrate solution and described X type molecular sieve is 2-20: 100.
6, according to the preparation method of the described petroleum spirit treating adsorbent of claim 1, wherein, the drying temperature in the step 3) is 110 ℃, and be 2 hours time of drying.
7, according to the preparation method of the described petroleum spirit treating adsorbent of claim 1, wherein, the maturing temperature in the step 4) is 500 ℃, and roasting time is 5 hours.
8, according to the preparation method of claim 1 or 2 described petroleum spirit treating adsorbents, wherein, described X type molecular sieve is 10X or 13X molecular sieve.
9, the petroleum spirit treating adsorbent that obtains of the preparation method of one of a kind of claim 1-8.
10, a kind of petroleum spirit treating adsorbent of claim 9 is used for 6# and 120# petroleum spirit deolefination and aromatic hydrocarbons at normal temperatures.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101142392A CN100404647C (en) | 2005-10-21 | 2005-10-21 | Petroleum solvent oil refining adsorbent, and its preparing method and use |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101142392A CN100404647C (en) | 2005-10-21 | 2005-10-21 | Petroleum solvent oil refining adsorbent, and its preparing method and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1891792A true CN1891792A (en) | 2007-01-10 |
| CN100404647C CN100404647C (en) | 2008-07-23 |
Family
ID=37596994
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101142392A Expired - Fee Related CN100404647C (en) | 2005-10-21 | 2005-10-21 | Petroleum solvent oil refining adsorbent, and its preparing method and use |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100404647C (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103752266A (en) * | 2014-01-30 | 2014-04-30 | 中国石油大学(北京) | Bimetallic mineral spirit refining adsorbent and preparation method and application thereof |
| CN103752271A (en) * | 2014-01-30 | 2014-04-30 | 中国石油大学(北京) | Mineral spirit refining adsorbent and preparation method thereof |
| CN103769046A (en) * | 2014-01-30 | 2014-05-07 | 中国石油大学(北京) | Double-molecular-sieve petroleum solvent oil refined adsorbent as well as preparation method and application thereof |
| CN105289481A (en) * | 2015-09-08 | 2016-02-03 | 山东成泰化工有限公司 | Solvent oil refined adsorbent and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DD229424A1 (en) * | 1984-11-29 | 1985-11-06 | Zeitz Hydrierwerk | METHOD FOR THE ADSORPTIVE REFINING OF MINERAL OIL COMPONENTS |
| CN1478863A (en) * | 2002-10-25 | 2004-03-03 | 中国石油化工股份有限公司 | Desulfur adsorber used for refined light oil product and its preparation method |
-
2005
- 2005-10-21 CN CNB2005101142392A patent/CN100404647C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103752266A (en) * | 2014-01-30 | 2014-04-30 | 中国石油大学(北京) | Bimetallic mineral spirit refining adsorbent and preparation method and application thereof |
| CN103752271A (en) * | 2014-01-30 | 2014-04-30 | 中国石油大学(北京) | Mineral spirit refining adsorbent and preparation method thereof |
| CN103769046A (en) * | 2014-01-30 | 2014-05-07 | 中国石油大学(北京) | Double-molecular-sieve petroleum solvent oil refined adsorbent as well as preparation method and application thereof |
| CN103752266B (en) * | 2014-01-30 | 2015-11-11 | 中国石油大学(北京) | A kind of bimetallic white spirit treating adsorbent and its preparation method and application |
| CN103769046B (en) * | 2014-01-30 | 2015-12-02 | 中国石油大学(北京) | A kind of bimolecular sieve white spirit treating adsorbent and its preparation method and application |
| CN105289481A (en) * | 2015-09-08 | 2016-02-03 | 山东成泰化工有限公司 | Solvent oil refined adsorbent and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100404647C (en) | 2008-07-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8425764B2 (en) | Process for producing petroleum oils with ultra-low nitrogen content | |
| CN1049918C (en) | Mercury removal from liquid hydrocarbon fraction | |
| KR101320813B1 (en) | Process for the desulfurization of gasolines comprising a desulfurization by adsorption of the light fraction and a hydrodesulfurization of the heavy fraction | |
| CN105969422B (en) | A kind of method of adsorbing separation production solvent naphtha | |
| CN101903497A (en) | Process for upgrading whole crude oil to remove nitrogen and sulfur compounds | |
| CN105080592A (en) | Aromatic olefin-reducing catalyst and use thereof | |
| CN107866285A (en) | A kind of renovation process of isomerization dewaxing catalyst | |
| CN1863753A (en) | Diisobutylene process | |
| CN101173192B (en) | Desulfurization method for diesel oil | |
| CN1891792A (en) | Petroleum solvent oil refining adsorbent, and its preparing method and use | |
| CN1292050C (en) | Method for separating normal alkane from full fraction naphtha | |
| CN101619240A (en) | Method for producing aromatic hydrocarbon solvent oil by using pyrolysis gasoline | |
| CN103752271B (en) | A kind of white spirit treating adsorbent and preparation method thereof | |
| CN101085936A (en) | Method for preparing thermal conductive oil by using coal liquefied oil | |
| CN111996029A (en) | C6~C10Method for purifying mixed aromatic hydrocarbon | |
| CN1064390C (en) | Double-solvant extraction for inferior paraffin base oil | |
| CN107362834B (en) | Treatment method of in-use continuous reforming catalyst | |
| CN107937014B (en) | Crack C9+Hydrogen solvent naphtha is added to take off naphthalene method and low naphthalene aromatic solvent naphtha | |
| KR100651356B1 (en) | Method for removing impurities from heavy hydrocarbon and deasphalt oil | |
| CN102557852B (en) | Method for extracting and removing dimethyl disulfide in refinery carbon tetrachloride | |
| CN1940019A (en) | Method for improving asphalt-removing oil output and decreasing solvent accounting simultaneously | |
| CN114832772B (en) | Mesoporous molecular sieve adsorbent and preparation method thereof | |
| WO2007066915A1 (en) | Environment-friendly hydrocarbon solvent composition removed normal hexane | |
| CN103752266A (en) | Bimetallic mineral spirit refining adsorbent and preparation method and application thereof | |
| CN104017602A (en) | Reformed pre-hydrogenated topped oil preprocessing method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |