CN1084548A - A kind of hydrogenation of petroleum resin preparation method of solvent - Google Patents
A kind of hydrogenation of petroleum resin preparation method of solvent Download PDFInfo
- Publication number
- CN1084548A CN1084548A CN 92110948 CN92110948A CN1084548A CN 1084548 A CN1084548 A CN 1084548A CN 92110948 CN92110948 CN 92110948 CN 92110948 A CN92110948 A CN 92110948A CN 1084548 A CN1084548 A CN 1084548A
- Authority
- CN
- China
- Prior art keywords
- hydrogenation
- solvent
- petroleum resin
- aromatic hydrocarbons
- preparation
- 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.)
- Pending
Links
Landscapes
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
A kind of hydrogenation of petroleum resin is characterized in that adopting the C of catalytic reforming by-product with the preparation method of solvent
9Aromatic hydrocarbons or cracking of ethylene C
9Heavy aromatics is the raw material of preparation hydrogenation of petroleum resin with solvent, and its boiling range is 150～200 ℃, and the preparation method is as follows: the C of catalytic reforming or steam cracking by-product
9Aromatic hydrocarbons, have hydrogenation catalyst in the presence of to adopt temperature of reaction be 150～280 ℃, pressure is 1.0～MPa, air speed 0.1～0.2h
-1, the condition of the volume ratio 1000～3000: 1 of hydrogen and C9 is carried out shortening.Distill on water distilling apparatus then and cut 140-200 ℃ of fraction oil, 90-95% of some raw material accounts for 5～10% less than 140 ℃ of fractions, calls in 5～15% C in 140-200 ℃ of fraction oil that distillation obtains
9Aromatic hydrocarbons makes the hydrogenation of petroleum resin solvent.
Description
The present invention relates to the preparation method of a kind of hydrogenation of petroleum resin, belong to the hydrogenation of petroleum resin field with solvent.
In the hydrogenation of petroleum resin process, generally be that solid resin is dissolved in the solvent with finite concentration, through heating, being mixed into hydrogenator with hydrogen, hydrogenator can be the batch still formula, can be continuous fixed bed also, material be after cooling off, telling hydrogen behind the hydrogenation, solvent steams with the distillatory way and recycles, and steams to such an extent that hydrogenated petroleum resin goes moulding and packing.
United States Patent (USP) 3,442,877(1969), 3,484,421(1969) and 3,701,760(1972) announced the hydrogenation of petroleum resin technology, employing be continuous fixed bed hydrogenation technology, the solvent of employing is a normal heptane, hexanaphthene, isoparaffin and mineral spirits.Its dissolving resin concentration is no more than 30%, generally 20～30%.The flat 1-190704(1989 of Japanese Patent) announced the fixed bed hydrogenation technology that (does not adopt solvent) under the petroleum resin molten state, this technology is to make petroleum resin (more than 200 ℃) fusing under comparatively high temps, keeps certain temperature to carry out hydrogenation then.
Adopt above-mentioned prior art solvent to carry out adding hydrogen into resin, because material concentration is lower, influenced the processing power of device, the solvent recuperation amount is bigger behind the hydrogenation, causes energy consumption to increase, and in addition, owing to adopt low material concentration, the hydrogenation resin degraded is more serious.Though hydrogenation can overcome above-mentioned shortcoming under the molten state, because whole hydrogenation system will be kept higher temperature, energy consumption increases, and has brought certain trouble to industrial operation.
Purpose of the present invention will overcome the shortcoming of above-mentioned existing solvent exactly, and the method for a kind of hydrogenation of petroleum resin with the preparation of solvent is provided.Utilize the inventive method, can prepare a kind of solvent of Cheap highly effective energy, this solvent is with the C of refinery catalytic reforming by-product
9Aromatic hydrocarbons or cracking of ethylene are paid the C of product
9Aromatic hydrocarbons is raw material, uses this solvent, and system need not tracing thermal-insulating and just can realize high density dissolving petroleum resin and carry out continuous fixed bed hydrogenation technology, thereby has overcome above-mentioned shortcoming.
The present invention adopts the C of catalytic reforming by-product
9Aromatic hydrocarbons or cracking of ethylene C
9Heavy aromatics is the raw material of preparation hydrogenation of petroleum resin with solvent, 150～200 ℃ of its boiling ranges, and concrete preparation method is as follows:
The C of catalytic reforming or steam cracking by-product
9Aromatic hydrocarbons, have hydrogenation catalyst in the presence of adopt 150～280 ℃ of temperature of reaction, pressure 1.0～10MPa, air speed 0.1～0.2h
-1, hydrogen and C
9The condition of volume ratio 1000～3000: 1 carry out hydrogenation, the hydrogenation purpose is with C
9Aromatic hydrocarbons changes into saturated naphthenic hydrocarbon, distills then to cut 140～200 ℃ of fraction oil on water distilling apparatus, accounts for 90～95% of raw material, accounts for 5～10% less than 140 ℃ of fractions.
In 140～200 ℃ of fraction oil that distillation obtains, call in 5～15% C
9Aromatic hydrocarbons makes hydrogenation solvent of the present invention.Because aromatic hydrocarbons is best to the solubility property of petrolatum, therefore call in C
9Aromatic hydrocarbons can increase the solubleness of petroleum resin on the one hand, can replenish the loss when solvent cycle is used in the hydrogenation of petroleum resin process on the other hand.The preparation hydrogenation catalyst that solvent adopted, catalyzer (for example: Harshaw Ni-0104 or the Engelhard 0.5% palladium/aluminum trioxide catalyst) hydrogenation unit that promptly carries nickel or year palladium also is to adopt the hydrogenation of petroleum resin reaction unit, and comparing with hydrogenation of petroleum resin is that processing condition are different.Can adopt hydrogenated products part round-robin method, the concentration of diluting aromatic hydrocarbons in the raw material, C in order to solve the exothermic heat of reaction problem in the hydrogenation process
9The ratio of aroamtic hydrocarbon raw material and circulation product is 1: 1～1: the 6(weight ratio).
With the hydrogenation of petroleum resin solvent of this method preparation, adopt original hydrogenation unit to need not to increase investment, the solvent loss C in the hydrogenation of petroleum resin process
9Aromatic hydrocarbons replenishes., raw material lower than production cost with other solvent phase is easy to get.Be used for hydrogenation of petroleum resin, can make the solubleness under the hydrogenating materials petroleum resin room temperature reach 30～70%, preferably under 40～60% concentration, carry out hydrogenation of petroleum resin.Can make the petroleum resin production cost reduce by 20～30%.Because hydrogenating materials adopts high density can reduce the amplitude that resin softening point is reduced because of the hydrogenation degraded.
The following examples are to the further specifying of the inventive method, rather than the restriction the spirit and scope of the present invention.
Embodiment 1
The C of catalytic reforming unit by-product
9Aromatic hydrocarbons carries out hydrogenation by nickel chromium triangle manganese/diatomite catalyzer (catalyzer that Jilin Chemical Industry Company calcium carbide factory produces), and the catalyst filling amount is 95g, reaction pressure 3.0MPa.240 ℃ of reactor inlet temperatures, 260 ℃ of focuses, weight space velocity 0.3h
-1, hydrogen and C
9The volume ratio of aromatic hydrocarbons 2000: 1, raw material C
9Aromatic hydrocarbons is 1: 1 with the ratio of the product that partly circulates.The naphthenic oil that hydrogenation obtains is that 95%(is heavy through the naphthenic oil yield that distillation cuts out less than 140～200 ℃ of remaining fractions of 140 ℃ of fractions (account for whole prod 5%)), wherein aromaticity content 1.5%(is heavy).
Embodiment 2
The naphthenic oil of 140 ℃～200 ℃ of fractions that obtain with embodiment 1 is called in 5% C
9Aromatic hydrocarbons makes hydrogenation of petroleum resin solvent of the present invention.With softening temperature on chip is 116 ℃, form and aspect 10(Fe-Co colorimetric) aromatic hydrocarbons petroleum resin (Liaoning Province Anshan Chem. Plant No.1 produce 871 resins), dissolve in this solvent, it is that 50%(is heavy that its solubleness sees Table 1(solubleness)).
Embodiment 3
The naphthenic oil of 140～200 ℃ of fractions that obtain with embodiment 1 is called in 15% C
9Aromatic hydrocarbons makes solvent of the present invention, and it is that 70%(is heavy that other operation sees Table 1(solubleness with embodiment 2 identical its solubleness)).
Embodiment 4
With 140～200 ℃ the cyclic hydrocarbon oil that embodiment 1 makes, do not call in C
9Aromatic hydrocarbons is directly as solvent, and other operation is identical with embodiment 2, and it is that 40%(is heavy that its solubleness sees Table 1(solubleness)).
Reference examples 1
In order to compare with solvent of the present invention, make solvent with normal heptane, other operation is identical with example 2, it is that 21%(is heavy that its solubleness sees Table 1(solubleness)).
Reference examples 2
In order to compare with solvent of the present invention, make solvent with cyclohexane, other operation is identical with embodiment 2, and solubleness sees Table 1.
Reference examples 3
Make solvent with mineral spirits, other operation is identical with embodiment 2, and solubleness sees Table 1
Application examples 1
Solvent with embodiment 2 preparations, and the identical petroleum resin of employing and embodiment 2, its resin concentration is that 50%(is heavy), hydrogenation unit is identical with embodiment 1 with catalyzer, hydrogenation conditions is 270 ℃ of temperature of reaction, reaction pressure 6.0MPa, hydrogen and resin volume ratio are 1500: 1, weight space velocity 0.12h
-1, its hydrogenation the results are shown in Table 2.
Application examples 2
With the solvent of example 4 preparations, the petroleum resin concentration that is used for hydrogenation is 40%, and other operation is identical with application examples 1, and hydrogenation the results are shown in Table 2.
Application examples 3
With the normal heptane solvent in the reference examples 1, the material resin concentration that is used for hydrogenation is that 20%(is heavy) other operation is identical with application examples 1, and hydrogenation the results are shown in Table 2.
Application examples 4
In order to investigate the use properties repeatedly of prepared solvent, use 140～200 ℃ naphthenic oil through using 34 times repeatedly, call in 5% C
9Aromatic hydrocarbons (identical with embodiment 2) is made solvent, and other operation is identical with application examples 1.
Table 1
Sequence number
[1]Solubleness % (weight) solvent boiling point or boiling range
2 50 140～200 ℃ of embodiment
3 70 140～200 ℃ of embodiment
4 40 140～200 ℃ of embodiment
Reference examples 1 21 98.4
Reference examples 2 30 80.7
Reference examples 3 25 145～190
Table 1 is annotated: [1] solubility test: get the 100g solvent, add in the 300ml wide-necked bottle, stir under the room temperature keeping, add gradually after pulverizing petroleum resin, each 2g that adds stirred 10 minutes, stopped to stir static 5 minutes, do not find precipitation, continue to add resin, repeat above-mentioned steps.Till precipitation occurring, at this moment write down the dissolving resin degree.
Table 1 embodiment shows, adopts the solvent of the present invention's preparation to call in C by control
9The amount of aromatic hydrocarbons can make to be executed 871 dissolving resin degree to reach 40～70%(heavy), higher by 30～50% than reference examples 1～3 dissolution with solvents degree in the table.In addition with reference examples 1～3 solvent phase than the present invention solvent boiling point than higher, be easy to realize the liquid phase hydrogenation of petroleum resin under the mitigation condition.
Table 2
| The application examples sequence number | The hydrogenation resin performance | ||||
| Softening ［1］℃ | Resin softening point fall ℃ behind the hydrogenation | Form and aspect ［2］(Saybolt) | The bromine valency ［3］gBr 2/100g | Thermostability ［4］Fe (c colorimetric) | |
| Application examples 1 application examples 2 application examples 3 application examples 4 | 103 100 94 102 | 13 16 22 14 | 30 30 30 30 | 1.45 1.51 1.41 1.49 | 4 4 4 4 |
Table 2 is annotated: [1] softening temperature is a ring and ball method, [2] form and aspect Saybolt: resin is made into 10% toluene solution and carries out colorimetric on the K131A colorimeter.[3] bromine valency: be ASTMD1159-66.[4] thermostability: resin sample is surveyed its Fe-Co form and aspect 175 ℃ of following thermal treatments 5 hours.
Table 2 application examples is the result show, compares with low material concentration (20%) application examples 3 that adopts normal heptane and adopts the softening temperature decline scope of 40% and 50% concentration resin little, descends 13 ℃ and 16 ℃ respectively.Application examples 4 and application examples 1 compare, and showing through the solvent after repeatedly using does not repeatedly influence the hydrogenation of petroleum resin effect.
Claims (1)
1, a kind of hydrogenation of petroleum resin is characterized in that adopting the C of catalytic reforming by-product with the preparation method of solvent
9Aromatic hydrocarbons or cracking of ethylene C
9Heavy aromatics is the raw material of preparation hydrogenation of petroleum resin with solvent, and its boiling range is 150～200 ℃, and the preparation method is as follows: the C of catalytic reforming or steam cracking by-product
9Aromatic hydrocarbons, have hydrogenation catalyst in the presence of to adopt temperature of reaction be 150～280 ℃, pressure is 1.0～10MPa, air speed 0.1～0.2h
-1, hydrogen and C
9The condition of volume ratio 1000～3000: 1 carry out shortening, on water distilling apparatus, distill then and cut 140-200 ℃ of fraction oil, the 90-95% of some raw material accounts for 5～10% less than 140 ℃ of fractions, calls in 5～15% C in the 140-200 ℃ of fraction oil that distillation obtains
9Aromatic hydrocarbons makes the hydrogenation of petroleum resin solvent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92110948 CN1084548A (en) | 1992-09-25 | 1992-09-25 | A kind of hydrogenation of petroleum resin preparation method of solvent |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 92110948 CN1084548A (en) | 1992-09-25 | 1992-09-25 | A kind of hydrogenation of petroleum resin preparation method of solvent |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1084548A true CN1084548A (en) | 1994-03-30 |
Family
ID=4945057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 92110948 Pending CN1084548A (en) | 1992-09-25 | 1992-09-25 | A kind of hydrogenation of petroleum resin preparation method of solvent |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1084548A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111373020A (en) * | 2017-11-23 | 2020-07-03 | 林德有限责任公司 | Method and system for obtaining polymerizable aromatic compounds |
-
1992
- 1992-09-25 CN CN 92110948 patent/CN1084548A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111373020A (en) * | 2017-11-23 | 2020-07-03 | 林德有限责任公司 | Method and system for obtaining polymerizable aromatic compounds |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP1993980B1 (en) | Lowering nitrogen-containing lewis bases in molecular sieve oligomerisation | |
| KR20190081905A (en) | Method for selective hydrogenation | |
| CN101332432B (en) | Load-type solid acid catalyst with selective oligomerisation for mixed C4 | |
| EP0674670A1 (en) | Dilute process for the preparation of ethylene/alpha-olefin copolymer using metallocene catalyst systems | |
| CN1315929A (en) | Composition for use in converting hydrocarbons, its preparation and use | |
| EP0619285B1 (en) | Process for producing gasolines and jet fuel from N-butane | |
| CN113939548B (en) | Process for preparing hydrogenated petroleum resin | |
| CN102718925B (en) | Preparation method of C5/C9 hydrocarbon resin | |
| CN1084548A (en) | A kind of hydrogenation of petroleum resin preparation method of solvent | |
| CN1736589A (en) | Selective hydrogenation catalyst and its application condition | |
| CN108238837B (en) | Method for producing low-carbon olefin by catalytic cracking | |
| CN1810742A (en) | Selective isobutene dimerizing process to prepare isooctene | |
| US9169169B2 (en) | Lowering nitrogen-containing Lewis bases in molecular sieve oligomerisation | |
| Girgis et al. | Catalytic hydroprocessing of simulated heavy coal liquids. 1. Reactivities of aromatic hydrocarbons and sulfur and oxygen heterocyclic compounds | |
| CN1060755C (en) | Process for producing ethylene and propene by catalytic thermal cracking | |
| CN112439433A (en) | Catalyst with hydrogenation and dimerization functions and preparation method and application thereof | |
| CN113559924B (en) | Ionic liquid catalyst and preparation method and application thereof | |
| CN1084521A (en) | A kind of method of hydrotreating of high raw material petroleum resin | |
| CN1172888C (en) | Process for preparing diisobutylene | |
| KR102638256B1 (en) | Method For Oligomerizing Ethylene Using Ejecter With Combined Venturi Tube | |
| CN1170858C (en) | Preparation method of low molecular weight polyisobutylene | |
| CN104277165B (en) | A kind of preparation method of low viscosity hydrogenated polyvinyl | |
| KR102695438B1 (en) | Continuous preparation method of hydrogenated petroleum resin | |
| CN107043637B (en) | A method of improving gasoline hydrodesulfurizationmethod selectivity | |
| CN1258503C (en) | Method for preparing isooctane |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C01 | Deemed withdrawal of patent application (patent law 1993) | ||
| WD01 | Invention patent application deemed withdrawn after publication |