CN105585665B - The method that Petropols continuously hydrogen adding prepares hydrogenated petroleum resin - Google Patents

Abstract

The invention belongs to Petroleum Processing Technology field, specially a kind of method that Petropols continuously hydrogen adding prepares hydrogenated petroleum resin.It uses the internal shell and tube reactor equipped with static mixing element, inlet setting gas distributor to be reacted, the following steps are included: by after the premixing of Petropols, solvent, catalyst and hydrogen, into shell and tube reactor, in 150~250 DEG C of temperature, it is reacted under 3.0~10.0MPa pressure, the residence time is 2~5hr；Wherein: the catalyst is modified skeletal nickel catalyst, and nickel content is 40~80wt%, and average pore size is 2.0~20.0nm, and the mass ratio between the Petropols, solvent and catalyst is 1:(1~3): (0.01~0.03)；The molar ratio of Petropols and hydrogen is 1:(2~5).This method reaction pressure is low, solvent consumption is few, and obtained hydrogenated petroleum resin is high-quality, and quality is stablized.

Description

The method that Petropols continuously hydrogen adding prepares hydrogenated petroleum resin

Technical field

The present invention relates to a kind of production methods by hydrogenated petroleum resin.In particular to continuously hydrogen adding production in a kind of industry The method of DCPD hydrogenated petroleum resin.

Background technique

It is also higher and higher to the quality requirement of Petropols with the continuous development in each field, wherein adhesive and sealing Agent application development, especially transparent pressure sensitive adhesive tape, outdoor sealant, disposable sanitary articles, medical adhesive tape, traffic paint with And the application of the modifying agent of polyolefin requires the good Petropols of lighter color, odorless and stability.Currently, on international market High-quality Petropols, coloration is less than 2#, and softening point generallys use hydrogenated petroleum resin technology, i.e. petroleum tree at 100 DEG C or more Unsaturated hydrocarbons in Petropols is changed into saturated hydrocarbons by the hydrogenated reaction of rouge, improves the form and aspect of Petropols, smell and resistance to The product of sign property.

It is in chain and cyclic structure since Petropols molecular weight is bigger, polymer molecule is stretched in catalyst surface, High spatial petroleum steric hindrance is formd, unsaturated bond hydrogenation reaction activation energy is high, so that reaction condition is become harsh, hydrogenation reaction needs It is carried out under the conditions of high temperature, high pressure and high activated catalyst.Hydrogenation of petroleum resin modification in the prior art mainly has slurry, fixation 3 kinds of bed, spray methods, autoclave hydrogenation technique (slurry and spray) use powdery Raney nickel, and pressure is lower, and fixed bed hydrogenation Technique uses loaded catalyst, and pressure is higher.CN200810084686.1 discloses the preparation of slurry autoclave hydrogenation of petroleum resin Technology, in a kettle, using modified skeletal nickel catalyst, preparation hydrogenation stone under conditions of pressure is 2.0-11.0MPa Oleoresin.But its dedicated hydrogenation reaction equipment design and the recycling of catalyst are extremely difficult, therefore slurry autoclave adds hydrogen industrial Change unsatisfactory.Japanese Huang Chuan chemical company develops fountain hydrogenation technique, industrializes in realization in 1985.Its technical process It is that grained catalyst is suspended on bubble cap plate, solves the problems, such as some of highly viscous fluid flowing using special designing, thus It can obtain preferably adding hydrogen effect under low pressure.This technique, which must separate adding hydrogen into resin with product, to be combined, and design is wanted Ask high, equipment investment is big, is difficult to control.

Therefore in the case where increasing production scale and simplifying the demand of technological operation, newly-built hydrogenation of petroleum resin device is mainly adopted With fixed bed hydrogenation technique.This hydrogenation technique can be one section or two sections and added using catalyst such as palladium, platinum and the nickel of support type Hydrogen, as JP61204210A uses supported palladium system and palladium-platinum group catalyst during adding hydrogen into resin.Patent US4629766 and US4540480 using gama-alumina load nickel sulfide and vulcanization tungsten catalyst, the technological reaction temperature be 280~290 DEG C, Reaction pressure 15-20Mpa, temperature of reactor are by being controlled with the heat carrier of reactor outer wall.

The uniformity of reactor temperature and reacting material concentration influences the quality of naval stores, since adding hydrogen into resin reacts For strong exothermal reaction, catalyst bed is easy to appear temperature runaway so as to cause catalyst inactivation, the prior art in catalytic hydrogenation In mostly dispose the method for heat-exchanger rig to remove the reaction heat largely generated using in hydrogenator, have a disadvantage in that it There is cooling uniformity certain limitation to cause there are still local excessive warming phenomenon in catalyst bed in reactor Partial catalyst inactivation, and Petropols easily react and generate colloid in the high-temperature region, this will all reduce naval stores Quality and yield.

Summary of the invention

In order to overcome the above-mentioned deficiencies of the prior art, the purpose of the present invention is to provide a kind of Petropols continuously hydrogen adding systems The method of standby hydrogenated petroleum resin, the reaction heat of adding hydrogen into resin process generation is removed by using more preferably heat-exchange method, Augmentation of heat transfer effect, guarantees the uniformity of reacting material concentration, to obtain good, stable product quality hydrotreated petroleum tree Rouge, while this method reaction pressure is low, solvent consumption is few, and energy consumption and equipment investment can be effectively reduced, and increases benefit.

Inventor it has been investigated that, hydrogenation of petroleum resin react when, reaction pressure is excessively high, reactor temperature and reactant The uniformity of material concentration can all influence the quality of naval stores, inventor by before Petropols raw material enters reactor by it It is pre-mixed with hydrogen, catalyst, can not only be sufficiently mixed raw material and hydrogen, catalyst, and enter band upon mixing Have when being reacted in the tubular reactor of static mixing element, catalyst can be kept to be suspended in reactor, keeps it entire Material is relatively uniform in reactor, increases the efficiency of hydrogenation reaction, to solve because raw material is uneven in the reactor It is even and the problem of influence hydrogenation reaction quality.Meanwhile the present invention uses existing reaction unit, without the use of the palladium of support type, platinum With the catalyst such as nickel (hydrogen is added to need higher pressure), and powdered modification Raney nickel is used, at lower pressures It can reach and preferably add hydrogen effect；In addition inventor is strengthened by the way of shell and tube by using inside reactor structure is changed Heat-transfer effect makes uniformity of temperature profile at the same section of inside reactor, and is removed in reaction process and generated by conduction oil Heat, avoid catalyst bed in catalytic hydrogenation and be easy to appear the phenomenon that temperature runaway is so as to cause catalyst inactivation.

It is the specific technical solution of the present invention below:

A kind of method that Petropols continuously hydrogen adding prepares hydrogenated petroleum resin uses internal equipped with static mixing member The shell and tube reactor that gas distributor is arranged in part, inlet is reacted, comprising the following steps: by Petropols, solvent, is urged After agent and hydrogen premixing, into shell and tube reactor, reacted at 150~250 DEG C of temperature, 3.0~10.0MPa pressure, Residence time is 2~5hr；Wherein: the catalyst is modified skeletal nickel catalyst, and nickel content is 40~80wt%, average Aperture is 2.0~20.0nm, and the mass ratio between the Petropols, solvent and catalyst is 1:(1~3): (0.01~ 0.03)；The molar ratio of Petropols and hydrogen is 1:(2~5).

Above-mentioned solvent is selected from any one of pentamethylene, hexamethylene, benzene, toluene or dimethylbenzene；It is furthermore preferred that solvent is first Benzene or dimethylbenzene.

Above-mentioned reaction temperature is 200~220 DEG C of temperature, and reaction pressure is 4.0~8.0MPa, the residence time is 3~ 4hr.The mass ratio of above-mentioned Petropols and solvent is 1: the molar ratio of (1~2), Petropols and hydrogen is 1: (3~4).

The beneficial effects of the present invention are: its one side is by carrying out premixing for raw material, catalyst and hydrogen and in pipe The method that formula reactor increases static cell solves the problems, such as raw material even concentration in hydrogenation process；On the other hand, Using shell and tube reactor augmentation of heat transfer, the mode that conduction oil moves heat avoids catalyst inactivation, substantially increases entire petroleum The effect and quality of adding hydrogen into resin；In addition, existing reaction unit is compared with fixed bed reactors, although all there is no catalyst point From can operate continuously, but the present invention is without the use of the catalyst such as palladium, platinum and the nickel of support type (adding hydrogen to need higher pressure), can Using powdered modification Raney nickel, it can reach preferably add hydrogen effect at lower pressures.Studies have shown that in the work Under the conditions of skill, for the conversion ratio of hydrogenation of petroleum resin up to 97% or more, softening point declines 6 DEG C or less.

Below by specific embodiment, the invention will be further described, the petroleum during hydrogenation of petroleum resin Adding hydrogen into resin conversion ratio definition are as follows:

Detailed description of the invention

Fig. 1 is the structural schematic diagram of shell and tube reactor used in embodiment.

Specific embodiment

(Shanghai Ni5388 enlightening sun chemical industry imports and exports limited public affairs to the skeletal nickel catalyst of Petropols raw material and solvent, modification Department) mixed with hydrogen through static mixing element after enter Fig. 1 shown in shell and tube reactor carry out hydrogenation reaction.Figure label: 1- The static mixer of the hybrid element containing SV；2- distributor；3- hot oil outlet；4- heat conductive oil inlet；5- reactor；6- contains JLF The static mixer of static mixing element.

In embodiment, Petropols raw material softening point is 130 DEG C, and color number is 7, and proportion is shown in Table 1, using ring and ball method GB/ 2294 analysis softening points, carry out Bromine Number analysis using iodimetric titration (SWB2301-62), calculate hydrogenation of petroleum resin reaction conversion ratio, It the results are shown in Table 2.

Table 1

Table 2

	Hydrogenation of petroleum resin conversion ratio %	Hydrogenation resin softening point DEG C
			Embodiment 1	97.0	124.0
Embodiment 2	97.2	125.8
			Embodiment 3	97.6	124.9
Embodiment 4	98.7	124.6
			Embodiment 5	98.1	125.0
Embodiment 6	98.5	125.3
			Embodiment 7	98.2	124.0
Embodiment 8	99.0	125.0
			Embodiment 9	98.1	125.0
Embodiment 10	97.2	125.8

Claims (7)

1. a kind of method that Petropols continuously hydrogen adding prepares hydrogenated petroleum resin, which is characterized in that it uses internal equipped with quiet The shell and tube reactor that gas distributor is arranged in state hybrid element, inlet is reacted, and is passed through conduction oil and removed reaction The heat generated in the process, comprising the following steps: after the premixing of Petropols, solvent, catalyst and hydrogen, into shell and tube Reactor reacts at 150~250 DEG C of temperature, 3.0~10.0MPa pressure, and the residence time is 2~5hr；Wherein: the catalysis Agent is modified skeletal nickel catalyst, and nickel content is 40~80wt%, and average pore size is 2.0~20.0nm, the Petropols, Mass ratio between solvent and catalyst is 1:(1~3): (0.01~0.03)；The molar ratio of Petropols and hydrogen is 1:(2 ~5).

2. the method according to claim 1, wherein the solvent be derived from pentamethylene, hexamethylene, benzene, toluene or Any one of dimethylbenzene.

3. method according to claim 1 or 2, which is characterized in that the solvent is toluene or dimethylbenzene.

4. the method according to claim 1, wherein the reaction temperature is 200~220 DEG C.

5. the method according to claim 1, wherein the reaction pressure is 4.0~8.0MPa.

6. the method according to claim 1, wherein the residence time is 3~4hr.

7. according to the method described in claim 1, it is characterized by: the mass ratio of the Petropols and solvent is 1: (1~ 2), the molar ratio of Petropols and hydrogen is 1: (3~4).