CN102453164B - Hydrogenation method for butane polymer - Google Patents
Hydrogenation method for butane polymer Download PDFInfo
- Publication number
- CN102453164B CN102453164B CN 201010513747 CN201010513747A CN102453164B CN 102453164 B CN102453164 B CN 102453164B CN 201010513747 CN201010513747 CN 201010513747 CN 201010513747 A CN201010513747 A CN 201010513747A CN 102453164 B CN102453164 B CN 102453164B
- Authority
- CN
- China
- Prior art keywords
- catalyst
- bed
- hydrogenation
- catalyzer
- raw material
- 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.)
- Active
Links
Abstract
The present invention discloses a hydrogenation method for a butane polymer. According to the present invention, under a hydrogenation process condition, reaction materials comprising a butane polymer raw material and hydrogen gas sequentially pass through at least two catalyst bed layers, wherein the catalyst in the first bed layer contains active components of copper and zinc, and the catalyst in the second bed layer is a high nickel hydrogenation catalyst or a noble metal hydrogenation catalyst. Compared to the prior art, with the present invention, the match of appropriate types of the catalysts is adopted, such that the service life of the catalyst can be effectively prolonged, and the economy of the butane polymer hydrogenation process is improved.
Description
Technical field
The present invention relates to a kind of hydrogenation method of butene polymers.
Background technology
Butene polymers mainly contains polybutene and polyisobutene, and butene polymers is a kind of important Speciality Petrochemicals raw material, except as the synthetic intermediate, also is widely used in modulation top-grade lubricating oil and extraordinary petroleum chemicals.For example, the lower molecular weight polybutene can reduce pollution as the machine oil component of two-stroke gasoline engine, belongs to the clean oil product.The intermediate molecular weight polybutene can significantly improve the oil body grade as lubricant tackifier.Polybutene and polyisobutene are easy to get because of raw material, low price, and the good face of shear stability obtains to be extensive use of.
Butene polymers is that the hydrocarbon raw material polymerization that contains butylene obtains, and contains isonomic other hydro carbons in the hydrocarbon raw material usually, generally contains ethene, propylene, butylene, iso-butylene, amylene etc., wherein based on the C4 component.Because unstripped gas contains the unsaturates of trace, maybe may contain oxygen, nitrogen, sulphur, chlorine, often have in the industrial goods polybutene like oily smell and gently amber.May contain impurity with two keys of other form because the end of butene polymers agent structure exists activated double bonds and its, its stability is also poor slightly.
It is that the poly-platform of catalyzer obtains that butene polymers is enough to haloid element usually, and this makes the by product that contains a small amount of haloid element in the product, has also influenced color and the smell of product.Sufficient especially low-molecular-weight polyisobutylene (PIB) has color and smell.These effects limit its under severe condition as in top-grade lubricating oil) application.
The hydrogenation polybutene has then overcome above-mentioned deficiency, the stability of product, color, smell aspects such as flavor and all be greatly improved, because its chemical property is stablized, especially resistance of oxidation is strong, decompose the no carbon deposit in back, product is colourless substantially, and is widely used in the machine oil of two-stroke gasoline engine, the occasion of industrial gear oil and other high-grade lubricating oil medium request harshness has obvious superiority.Simultaneously, it still keeps the original most characteristics of polybutene, and purposes is very extensive.
US3,100,808 disclose a kind of lower alkene polymers that will be formed by from two to five carbon atom olefinic monomer polymerizations of gained in petroleum refinery's gas, as butene polymers, and and then to such as the butene polymers hydrogenation, improved color, smell and heat, light stability and stability in storage.And there are not great effect in other Applied Physics characteristics of product.Wherein, molecular weight can be low to moderate 400 to 600, and is high to 20,000 even higher, can be by adding hydrogen purification, to improve aspect character such as color, smell and stability.
US4,061,780 discloses a kind of oil base cosmetic composition and purifying technique thereof.Described cosmetics oil is by containing iso-butylene or iso-butylene and 1-butylene, 2-butylene, 1,2-divinyl and 1, the mixture of one or more among the 3-divinyl, from 30 to 60 ℃ of temperature, polymerization prepares thick liquid polymer products in the presence of Knut Fridell technology and Lewis acid, sufficient especially polyisobutene.Saturated through underpressure distillation, hydrogenation, obtain the finished product through stripping or gac deodorizing or solvent extraction again.
US5,043,420 disclose a kind of cosmetic use molecular weight about 100 to 4000 have smell the flavor isobutene polymer deodorisation process, comprise: (a) described hydrogenation of polymer, be to arrive in the presence of about 700 Fahrenheit degrees and the catalyzer about 150, prepare saturated substantially hydrogenation isobutene polymer frowzy; (b) described hydrogenation polymkeric substance is used the indifferent gas air lift in temperature under at least 290 Fahrenheit degrees, be enough to carry out the described hydrogenation isobutene polymer of weight at least 2% weight, to remove the described compound frowzy of part, preparation is through the hydrogenation isobutene polymer of air lift; (c) with described hydrogenation isobutene polymer through air lift with attapulgite clay by touching to eliminate other malodorous compounds; (d) reclaim final isobutene polymer.
US5,177,277 disclose a kind of polybutene 150 to about 525 Fahrenheit degrees and the catalyzer hydrogenation, contain the hydrogenated polybutene of smelling the flavor material with generation, and then underpressure distillation removes and contains the flavor material, recycle silicon glue is handled.
In the decolouring deodorizing flavor method of above-described butene polymers, generally be by the saturated color of improving of hydrogenation,, remove all the other by absorption again and contain the flavor material or/and the smell material is removed gently, heavily contained in distillation by air lift.In the above method, the catalyzer that the hydrogenation process of mentioning adopts is molybdenum, nickel and precious metal.Practice shows that the activity stability of this type of catalyzer in butene polymers hydrogenation process is relatively poor, and running period is shorter, thereby makes Technological Economy relatively poor.
Summary of the invention
At the deficiencies in the prior art, the invention provides a kind of butene polymers method of hydrotreating, by adopting the cooperation of suitable kind catalyzer, can effectively prolong the work-ing life of catalyzer, improve the economy of hydrogenation technique.
Butene polymers method of hydrotreating of the present invention comprises following content: under the hydrogenation technique condition, the reaction mass that butene polymerization raw material and hydrogen constitute is successively by at least two beds, the catalyzer of first bed contains active ingredient copper and zinc, and the catalyzer of second bed is high nickel hydrogenation catalyst or noble metal hydrogenation catalyst.
In the inventive method, the butene polymerization raw material can be polybutene or polyisobutene, and its number-average molecular weight is 300～8000, can Individual existence or be dissolved in the lubricating oil, and its chlorinity is below 300mg/kg.
In the inventive method, the hydrogenation technique condition comprises: working pressure 0.1～20.0MPa, be preferably 2.0～15.0MPa, and 100～300 ℃ of temperature of reaction are preferably 150～260 ℃, volume space velocity 0.1～2.0h during the polybutene stock liquid
-1, be preferably 0.2～1.0h
-1, the volume ratio under hydrogen and the liquid phase feed standard state is 100: 1～2000: 1, be preferably 300: 1～1000: 1 (with claim hydrogen to oil volume ratio).The volume ratio of the first bed catalyst bed and the second bed catalyzer is 1: 2～1: 20, is preferably 1: 2～1: 6.
Among the present invention, the carrier of the first bed catalyzer and the second bed catalyzer is the porous refractory oxide, as aluminum oxide, silicon-dioxide, diatomite, clay etc., is preferably aluminum oxide.
The first bed catalyst activity component is preferably by weight: cupric oxide 4%～40%, zinc oxide 2%～40%, ferric oxide 0～20%.The pore volume of the first bed catalyzer is generally 0.2～1.0ml/g, and specific surface area is generally 30～300m
2/ g.
The second bed catalyzer can be high nickel hydrogenation catalyst, or noble metal hydrogenation catalyst.In catalyst weight, nickel content is 15%～50% in the high nickel hydrogenation catalyst.In catalyst weight, the content of platinum or palladium is 0.1%～5% in the noble metal catalyst.The pore volume of the second bed catalyzer is generally 0.3～1.0ml/g, and specific surface area is generally 30～200m
2/ g.
In the inventive method, the first bed catalyzer and the second bed catalyzer can be seated in the reactor, also can be seated in the different reactors.
The catalyzer that uses among the present invention can be selected the commodity that suit as required, also can prepare according to this area ordinary method.
Butene polymers behind the hydrogenation is further purified by at least a method in air lift, distillation, the absorption again, to remove trace impurity, guarantees quality product.
The inventive method is by adopting being used in combination of different properties catalyzer, the problem of catalyst stability deficiency in effective solution and the existing butene polymers hydrogenation process, can obviously prolong the work-ing life of catalyzer, reduce the financial loss that catalyst consumption and device are stopped work and caused, and protect and levy quality product.
Embodiment
Further specify the solution of the present invention and technique effect below by embodiment and comparative example, per-cent wherein is weight percentage.
Embodiment 1:
The hydrogenation technique that adopts: raw material enters the fixed bed hydrogenation reactor hydrogenation that is mounted with two beds after filtering, and (distillation of 0.133kPa～1.33kPa) is removed on a small quantity, and (0.2%～2%)＜300 ℃ cut and laboratory vacuum filtration obtain the finished product to hydrogenation products by decompression again.
Raw material is the low molecular weight polycaprolactone butylene, number-average molecular weight 1100.100 ℃ of viscosity 325mm
2/ s, GB6540 color 1.0#, bromine number 17.0.
The first bed catalyst activity component is that (oxidation system 20%, zinc oxide 12%, carrier are aluminum oxide to zinc processed, pore volume 0.6ml/g, specific surface area 130m
2/ g), second bed is that (nickel content 39%, aluminum oxide are carrier to high nickel hydrogenation catalyst, pore volume 0.45ml/g, specific surface area 80m
2/ g), first bed is 1: 6 with second bed volume ratio.
The hydrogenation technique condition is: working pressure 12MPa, 250 ℃ of temperature of reaction, volume space velocity 0.5h
-1With hydrogen to oil volume ratio 500: 1.
Product property: Saybolt color+30#, number-average molecular weight 1050.99%, 100 ℃ of viscosity 310-325mm of＞300 cut yields
2/ s.Bromine number 0.03～0.05.Smell flavor, do not have.
Hydropyrolysis experiment is through after 1000 hours, and product property is constant.
Reference examples: with embodiment 1 condition, the first bed catalyzer is identical with the second bed catalyzer, is high nickel hydrogenation catalyst.Initial production character is also identical as a result, but through after 400 hours, the Saybolt color is down to+28#, and after 700 hours, the Saybolt color is down to+25#.
Embodiment 2:
Oxygenation technology and raw material with embodiment 1 employing.
The first bed catalyst activity component is that (cupric oxide 20%, zinc oxide 12%, carrier are aluminum oxide to copper zinc, pore volume 0.6ml/g, specific surface area 150m
2/ g).The second bed catalyzer is that (palladium content 1.0%, carrier are aluminum oxide to palladium catalyst, pore volume 0.5ml/g, specific surface area 140m
2/ g).The volume ratio of the first bed catalyzer and the second bed catalyzer is 1: 6.
Processing condition are: 210 ℃ of working pressure 10MPa, temperature of reaction, volume space velocity 1.0h
-1With hydrogen to oil volume ratio 500: 1.
Product property: Saybolt color+30#, number-average molecular weight 1060.99%, 100 ℃ of viscosity 315-325mm of＞300 cut yields
2/ s.Bromine number 0.05～0.1.
Hydropyrolysis experiment 500 hours, product property is constant.
Reference examples: with embodiment 2 conditions, the first bed catalyzer is identical with the second bed catalyzer.Initial production character is identical as a result, and through 300 hours, the Saybolt color was down to+28#.
Embodiment 3:
Hydrogenation technique with embodiment 1 employing.
Raw material is the low molecular weight polycaprolactone butylene, number-average molecular weight 730.100 ℃ of viscosity 241mm
2/ s, GB6540 color 1.0#, bromine number 19.0.
The first bed catalyzer is identical with embodiment 1 with the second bed catalyzer, and the volume ratio of the first bed catalyzer and the second bed catalyzer is 1: 8.
The hydrogenation technique condition is: 210 ℃ of working pressure 8MPa, temperature of reaction, volume space velocity 1.5h
-1With hydrogen to oil volume ratio 500: 1.
Product property: Saybolt color+30#, number-average molecular weight 725.99%, 100 ℃ of viscosity 235-240mm of＞300 cut yields
2/ s.Bromine number 0.01～0.05.
Hydropyrolysis experiment is through after 300 hours, and product property is constant.
Reference examples: with embodiment 3 conditions, the first bed catalyzer is identical with the second bed catalyzer.Initial production character is identical as a result, and through 150 hours, the Saybolt color was down to+28#.
Embodiment 4:
Hydrogenation technique with embodiment 1 employing.
Raw material is middle molecular weight polyisoprene butylene, number-average molecular weight 11000.With long-pending lubricating oil (white mineral oil) the melt into mixed solution of diploid.100 ℃ of viscosity 330mm of mixed solution
2/ s, GB6540 color 1.0#, bromine number 2.1.
The second bed catalyzer is copper zinc-iron (ferric oxide 15%, carrier are aluminum oxide for oxidation system 30%, zinc oxide 21%) with embodiment 1, the first bed catalyst activity component, and the volume ratio of the first bed catalyzer and the second bed catalyzer is 1: 15.
The hydrogenation technique condition is: 250 ℃ of working pressure 15MPa, temperature of reaction, volume space velocity 0.5h
-1With hydrogen to oil volume ratio 800: 1.
Product property: Saybolt color+30# before 500 hours, 100 ℃ of viscosity 315mm
2/ s.Bromine number 0.03.
Reference examples: with embodiment 4 conditions, the first bed catalyzer is identical with the second bed catalyzer.Initial production character is identical as a result, and through 300 hours, the Saybolt color was down to+28#.
Claims (7)
1. the method for hydrotreating of a butene polymers, it is characterized in that: under the hydrogenation technique condition, the reaction mass that butene polymerization raw material and hydrogen constitute is successively by at least two beds, the catalyzer of first bed contains active ingredient copper and zinc, and the catalyzer of second bed is high nickel hydrogenation catalyst or noble metal hydrogenation catalyst;
The hydrogenation technique condition comprises: working pressure is 0.1～20.0MPa, and temperature of reaction is 100～300 ℃, and volume space velocity is 0.1～2.0h during the polybutene stock liquid
-1, the volume ratio under hydrogen and the liquid phase feed standard state is 100: 1～2000: 1;
The first bed catalyst activity component is by weight: cupric oxide 4%～40%, zinc oxide 2%～40%, ferric oxide 0～20%; The second bed catalyzer is high nickel hydrogenation catalyst, or noble metal hydrogenation catalyst; In catalyst weight, nickel content is 15%～50% in the high nickel hydrogenation catalyst; In catalyst weight, the content of platinum or palladium is 0.1%～5% in the noble metal catalyst; The volume ratio of the first bed catalyzer and the second bed catalyzer is 1: 2～1: 20.
2. in accordance with the method for claim 1, it is characterized in that: the butene polymerization raw material is polybutene or polyisobutene, and its number-average molecular weight is 300～8000.
3. according to claim 1 or 2 described methods, it is characterized in that: butene polymerization raw material Individual existence or be dissolved in the lubricating oil.
4. according to claim 1 or 2 described methods, it is characterized in that: the chlorinity of butene polymerization raw material is below 300mg/kg.
5. in accordance with the method for claim 1, it is characterized in that: the hydrogenation technique condition comprises: working pressure is 2.0～15.0MPa, and temperature of reaction is 150～260 ℃, and volume space velocity is 0.2～1.0h during the polybutene stock liquid
-1, the volume ratio under hydrogen and the liquid phase feed standard state is 300: 1～1000: 1.
6. it is characterized in that in accordance with the method for claim 1: the volume ratio of the first bed catalyzer and the second bed catalyzer is 1: 2～1: 6.
7. it is characterized in that in accordance with the method for claim 1: the butene polymers behind the hydrogenation is further purified by at least a method in air lift, distillation and the absorption.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010513747 CN102453164B (en) | 2010-10-14 | 2010-10-14 | Hydrogenation method for butane polymer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010513747 CN102453164B (en) | 2010-10-14 | 2010-10-14 | Hydrogenation method for butane polymer |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102453164A CN102453164A (en) | 2012-05-16 |
| CN102453164B true CN102453164B (en) | 2013-10-09 |
Family
ID=46036883
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010513747 Active CN102453164B (en) | 2010-10-14 | 2010-10-14 | Hydrogenation method for butane polymer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102453164B (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4061780A (en) * | 1972-12-20 | 1977-12-06 | Nichiyu Kagaku Co., Ltd. | Cosmetic oil containing isobutylene |
| CN101811042A (en) * | 2009-02-25 | 2010-08-25 | 中国中化股份有限公司 | Selective hydrogenation catalyst and preparation method and application thereof |
-
2010
- 2010-10-14 CN CN 201010513747 patent/CN102453164B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4061780A (en) * | 1972-12-20 | 1977-12-06 | Nichiyu Kagaku Co., Ltd. | Cosmetic oil containing isobutylene |
| CN101811042A (en) * | 2009-02-25 | 2010-08-25 | 中国中化股份有限公司 | Selective hydrogenation catalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102453164A (en) | 2012-05-16 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP2958707B2 (en) | Method for improving thermal stability of synthetic lubricating oil | |
| CN1107547C (en) | Selective hydrogenation catalysts containing palladium and at least one element selected among tin and lead | |
| KR950032300A (en) | Method for producing polyisobutene | |
| JP2000516665A (en) | Ethylene-α-olefin polymer, production and use | |
| CN101389670A (en) | Process for preparation of polyisobutylene whose content of terminal double bonds is more than 50% from an industrial C4 hydrocarbon stream comprising 1-butene, 2-butene and isobutene | |
| JPH03505469A (en) | Phosphonate adducts of olefinic lubricants with enhanced properties | |
| CN1160284C (en) | Process for the hydrogenation of phenyl acetylene in a styrene-containing medium with the aid of a catalyst | |
| CN102451694A (en) | Hydrogenation dethiolizing catalyst, preparation method thereof and application thereof | |
| CN101121899B (en) | Selectivity hydrogenation method for whole fraction crack petroleum | |
| FR2864102A1 (en) | Catalyst for selective hydrogenation of olefins, especially dienes, comprises cobalt and/or nickel, molybdenum and/or tungsten and alkali metal on an alumina support | |
| CA2179390A1 (en) | Novel hydrocarbon lube and distillate fuel additive | |
| US5191139A (en) | Process for oligomerizing olefins using sulfate-activated group IV oxides | |
| CN102453164B (en) | Hydrogenation method for butane polymer | |
| CN111013611B (en) | Preparation method of olefin polymerization catalyst and preparation method of poly alpha-olefin base oil | |
| CN1060755C (en) | Process for producing ethylene and propene by catalytic thermal cracking | |
| CN110551522B (en) | Method for preparing lubricating oil base oil | |
| CN112125993B (en) | Method for liquid-phase hydrofining of polyvinyl ether | |
| JP4863186B2 (en) | Process for producing olefin polymer | |
| CN101805239A (en) | By the selection hydrofining of acetylene being contained the aromatic fraction of acetylene | |
| CN110607199B (en) | Method for removing impurities by hydrogenating polyvinyl ether | |
| EP0413795A1 (en) | Synthetic lube composition and process. | |
| CA1318634C (en) | Two step process for the obtainment of white oils | |
| CN112725017B (en) | Process method for directly synthesizing high-performance high-viscosity base oil by polymerization of low-carbon olefin | |
| CN102229815B (en) | Method for preparing low carbon olefin by deep catalytic cracking of inferior oil | |
| US2379410A (en) | Catalytic production of hydrogenated polymers |
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 |