CN105368494A - A production process of novel environmental-friendly biological rubber-tyre filling oil - Google Patents

Abstract

The invention mainly provides a production process of novel environmental-friendly biological rubber-tyre filling oil. The process combines hydrogenation, extraction and fractionation, and introduces a new idea of preparing rubber filling oil by adopting mineral oil and vegetable oil as raw materials. Conventional devices in the processing industry at present can be utilized. The process is mature in technique, simple in production procedures and low in cost. The produced environmental-friendly rubber filling oil allows the environmental protection performance of oil products to meet requirements of the European Union and is good in compatibility with rubber. Main indexes of the produced filling oil meet quality index requirements of environmental-friendly tyre oil.

Description

A kind of production technique of new type environmental protection biologic rubber tire filling oil

Technical field

The present invention relates to rubber additive technical field, specifically, be a kind of production method of environment protection biological rubber tire filling, the filling for various rubber is processed.

Background technology

Rubber filling oil is a kind of special type for the production of oil-extended rubber oil.After rubber is oil-filled, processing characteristics and use properties can improve, and add Rubber Yield simultaneously, reduce costs.China's natural rubber limits throughput, synthetic rubber occupies significant proportion in rubber industry.Along with the progress of China's synthetic rubber technology, the raising of output, the output of oil-extended rubber is also increasing sharply, and therefore also grows with each passing day to the demand of rubber filling oil.

But the polycyclic aromatic hydrocarbon compounds (PCA) such as anthracene, phenanthrene contained in rubber filling oil, by European Union be included into can be carcinogenic CMR class material.In REACH regulation annex, clear and definite and strict regulation is made to PCA content in the product, PCA < 3% in extending oil.From 1 day January in 2010, not meeting rubber oil that European Union 2005/69/EC specifies can not direct marketing and using in tire.And press REACH rules and regulations, PAHs content total in tire should be less than 0.1% (i.e. 1000mgkg-1) of tire quality.

Chinese patent CN1298901 discloses a kind of unsaturated rubber extending oil.This unsaturated rubber extending oil adopts the light base oil that Saybolt colour number is 0 ~+30, flash-point is 160 DEG C ~ 350 DEG C to be raw material, with plasticising solubilizing agent for additive, described plasticising solubilizing agent is the mixture of a kind of of the ester class with plasticising solubilising function and multiple ester thereof, its adding proportion is 1% ~ 70% (weight), the extending oil that the present invention produces fills colloidality energy and light, good heat stability, and nontoxic.

Chinese patent CN1752182 discloses a kind of production method of aromatic hydrocarbon rubber filling oil, send after coal tar fraction and hydrogen mixing into hydrogenator, with Mo-Ni-P catalyst for hydro-upgrading contact reacts under certain reaction conditions, remove the sulphur in coal tar fraction, nitrogen impurity and colloid, bituminous matter; Afterwards hydrogenation reaction product is sent into gas delivery and stable system, isolate hydrogen, dry gas, hydrogen sulfide and ammonia and liquefied gas, obtain product liquid; Finally this product liquid is sent into separation column and carry out fractionation, cutting, obtain aromatic hydrocarbon rubber filling oil.

Use environment-friendly rubber extending oil to reduce and produce and use carcinogenic phenyl ring in rubber process to the harm of human body, to be the trend of rubber filling oil development.Current China can't self-produced environment-friendly rubber extending oil, and import oil product is expensive, and source can not ensure again completely, and the stable supply of environment-friendly rubber extending oil has become the bottleneck that restriction environment-friendly type oil-extended rubber is produced.

The rubber filling oil substitute of current domestic laboratory development, mainly contains two kinds of techniques, and a kind of employing denitrogenation-carclazyte technique, another kind takes high-pressure hydrogenation technology, and technique aromatic hydrocarbons being converted to cycloalkanes processes.Take the product polycyclic aromatic hydrocarbons of this two kinds of techniques development and enablely reach European Union requirements, but due to aromaticity content low, with the poor compatibility of rubber, can not as the substitute of rubber filling oil.

Summary of the invention

The object of the invention is to overcome the deficiencies in the prior art, a kind of production method of environment protection biological rubber tire filling is provided.

The object of the invention is to be achieved through the following technical solutions: a kind of production method of environment protection biological rubber tire filling, comprises the following steps:

(1) by stock oil in vacuum tightness be underpressure distillation under the condition of 600-700mmHg, temperature 200-300 DEG C, get the cut of 250-270 DEG C, add hydrogenation catalyst and carry out contact reacts, impurity in removing raw material, reaction conditions is: hydrogen pressure is 2.5-7MPa, temperature of reaction 300-350 DEG C, flow is 7-11m3/h, hydrogen to oil volume ratio 500-700, derives reactor by reaction product after reaction;

(2) above-mentioned reaction product is inserted extraction tower solvent and carry out extracting, reaction conditions is: temperature 50-70 DEG C, molten

The mass ratio of agent and above-mentioned reaction product is 3: 1 ~ 6: 1, and extraction times is 1-3h, obtains extract product from tower top;

(3), after removing the solvent in extract product, enter in separation column and carry out fractionation, obtain more than 300 DEG C cuts, obtain environment protection biological rubber tire filling of the present invention.

Preferably, the stock oil in (1) step is the combination of mineral oil and vegetables oil, and the ratio of its mineral oil in fluid in stock oil is 50-100%, and the ratio of vegetables oil is 0-50%.

Preferably, (1) hydrogenation catalyst in step can be conventional hydrogenation catalyst, also can be Mo-Ni-P hydrogenation catalyst, wherein, in oxide dry basis, MoO3 accounts for the 19-30w% of total catalyst weight, and NiO accounts for the 7-10w% of total catalyst weight, P2O5 accounts for the 2-5w% of total catalyst weight, and all the other are amorphous silicic acid alumina supporter.

Preferably, the solvent in (2) step be selected from furfural, sherwood oil, phenol, ether, tetramethylene sulfone, dimethyl sulfoxide (DMSO), dimethyl methyl phthalein amine or N monomethyl pyrrolidone one or more.

Preferably, the separation column in (3) step is atmospheric fractional tower, and operational condition adopts conventional operational condition.

Compared with prior art, positively effect of the present invention is:

1, when when rubber filling oil demand constantly increases, oil supply day is becoming tight, the present invention produces the open raw material sources newly of rubber filling oil.Propose idea mineral oil being prepared together with vegetables oil rubber filling oil as stock oil, and confirm by experiment really can obtain with this stock oil the extending oil meeting international requirement.

2, the inventive method is based on the method for making of current domestic relevant rubber filling oil, proposes a kind of production method of rubber filling oil of novelty, and conbined usage is carried out in hydrogenation-extracting-fractionation; Can utilize device conventional in current processing industry, mature technology, Production Flow Chart is simple, and cost is lower.

3, it is 910-950kg/m3 that the rubber filling oil that the inventive method is produced records density through GB/T1884 method, 40 DEG C of viscosity are 200-230mm2s-1, sulphur content is lower than 300 μ g/g, CA value is 15-20%, PCA <'s 2.3%, every leading indicator all meets the quality index requirement of environmental tire oil.

4, the environment-friendly rubber extending oil adopting present method to produce not only can make the oil product feature of environmental protection reach European Union requirements, and has good consistency with rubber; It is high that the solvent recovery process adopted has solvent recovering rate, and condition is easy to the advantages such as realization.

Embodiment

The production method of environment protection biological rubber tire filling of the present invention, comprises the following steps:

(1) by stock oil in vacuum tightness be underpressure distillation under the condition of 600-700mmHg, temperature 200-300 DEG C, get the cut of 250-270 DEG C, add hydrogenation catalyst and carry out contact reacts, impurity in removing raw material, reaction conditions is: hydrogen pressure is 2.5-7MPa, temperature of reaction 300-350 DEG C, flow is 7-11m3/h, hydrogen to oil volume ratio 500-700, derives reactor by reaction product after reaction.Wherein, stock oil is made up of mineral oil and vegetables oil, and mineral oil refers to the base oil extracted from oil by physics distillating method, and impurity is more.Vegetables oil is the fat from plant seed, pulp and other extracting section gained, also referred to as Vegetable oil lipoprotein.Hydrogenation reaction adopts conventional fixed bed hydrogenation reactor, and the operating method adopting one way to pass through.After stock oil cut mixes with hydrogen, enter reactor from hydrogenator top, flow downward in hydrogenator _ _ react rear reaction product to derive from the bottom of hydrogenator.

(2) above-mentioned reaction product is inserted extraction tower solvent and carry out extracting, reaction conditions is: temperature 50-70 DEG C, the mass ratio of solvent and above-mentioned reaction product is 3: 1 ~ 6: 1, and extraction times is 1-3h, obtains extract product from tower top; Wherein, extraction tower is conventional petrochemical complex extraction tower, and reaction product enters from extraction tower bottom, solvent enters from extraction tower top, and from bottom to top, solvent from top to bottom for reaction product, counter current contact, at given extraction temperature with in the time, carries out extracting to reaction product; The solvent of extracting be selected from furfural, sherwood oil, phenol, ether, tetramethylene sulfone, dimethyl sulfoxide (DMSO), dimethyl methyl phthalein amine or N monomethyl pyrrolidone one or more.Extract product is discharged from extraction tower top.

(3), after removing the solvent in extract product, enter in separation column and carry out fractionation, obtain more than 300 DEG C cuts, obtain environment protection biological rubber tire filling of the present invention.Remove the solvent in extract product by ordinary method, in separation column, carry out fractionation subsequently, finally obtain biological rubber filling tires of the present invention oil.

The embodiment of the production method of a kind of environment-friendly rubber extending oil of the present invention is below provided.

Embodiment 1

Small test device is tested.Hydrogenator is 100ml fixed bed hydrogenation reactor; Fractionation uses the true boiling point distillation device with 17 blocks of theoretical trays.Stock oil is respectively mineral oil, mineral oil and vegetables oil (1: 1), mineral oil and vegetables oil (3: 1), mineral oil and vegetables oil (6: 1).The Mo-Ni-P hydrogenation catalyst be supported on amorphous aluminum silicate steroidal is loaded in 100ml fixed bed hydrogenation reactor, its MoO3 accounts for the 20w% of total catalyst weight, NiO accounts for the 9.2w% of total catalyst weight, and P2O5 accounts for the 2.9w% of total catalyst weight, and all the other are amorphous aluminum silicate steroidal.

The pore volume of catalyzer is 0.38ml/g, specific surface is 363m2/g, spherical.This catalyzer adopts ordinary method to carry out prevulcanized before use, after it is activity stabilized, carry out process condition test again.In operating process, stock oil cut is mixed with hydrogen and enters from hydrogenator top, react with catalyst come into contact.The mode that test adopts one way to pass through carries out hydrogenation.After reaction, reaction product derives from reactor lower part, enters extraction tower after being cooled to normal temperature.

Reaction product enters from extraction tower bottom, and solvent enters from extraction tower top, and reaction product from bottom to top, from top to bottom, counter current contact is 6: 1 at the mass ratio of temperature 50 C, solvent and above-mentioned reaction product to solvent, extraction times is under the condition of 3h, carries out extracting to reaction product; The solvent of extracting is furfural.On extraction tower top, be stripped of the polycyclic aromatic hydrocarbons in reaction product, form extract product, discharge from extraction tower top.

Adopt the solvent furfural in conventional means removing extract product, the extract product after desolventizing is sent into true boiling point distillation device and carries out fractionation.Fractionation discard the lighting end of less than 300 DEG C in the apparatus, obtains the cut of more than 300 DEG C, namely obtains biological rubber filling tires of the present invention oil.

The product property that embodiment 1 obtains is see table 1.In order to investigate contrast, in table 1, list the typical physico-chemical property of the environment-friendly rubber extending oil of foreign recommended in the lump.

Table 1

Project	Mineral oil	Mineral oil and planting	Thing oil (1	∶	1)
						Colourity	9.0	8.1	8.3	8.6	8.0
Density kg/m3	950	925	937	943	939
						40 DEG C of viscosity	mm2·s-1	230	205	214	221
Flash-point DEG C	270	261	265	269	264
						Pour point DEG C	35	28	31.1	33	＞
Refractive index	1.5784	1.5312	1.5411	1.5741	1.52
						Viscosity gravity constant	VGC	0.89	0.84	0.859	0.874
Carbon type analysis CA	％	20.0	16.0	18.0	17.0
						PCA	Content %	2.1	2.0	2.05	2.12

As can be seen from Table 1, the biological rubber filling tires oil density that embodiment 1 obtains is 910-950kg/m3,40 DEG C of viscosity are 200-230mm2s-1, sulphur content is lower than 300 μ g/g, CA value is 15-20%, PCA <'s 2.3%, and every leading indicator all meets the quality index requirement of environmental tire oil, good stability, nonpoisonous and tasteless.

Claims (5)

1. a production method for environment protection biological rubber tire filling, comprises the following steps:

(1) by stock oil in vacuum tightness be underpressure distillation under the condition of 600-700mmHg, temperature 200-300 DEG C, get the cut of 250-270 DEG C, add hydrogenation catalyst and carry out contact reacts, impurity in removing raw material, reaction conditions is: hydrogen pressure is 2.5-7MPa, temperature of reaction 300-350 DEG C, flow is 7-11m3/h, hydrogen to oil volume ratio 500-700, derives reactor by reaction product after reaction;

(2) above-mentioned reaction product is inserted extraction tower solvent and carry out extracting, reaction conditions is: temperature 50-70 DEG C, the mass ratio of solvent and above-mentioned reaction product is 3: 1 ~ 6: 1, and extraction times is 1-3h, obtains extract product from tower top;

(3) after removing the solvent in extract product, enter in separation column and carry out fractionation, obtain more than 300 DEG C cuts, obtain environment protection biological rubber tire filling of the present invention, wherein, the ratio of mineral oil in stock oil is 50% to 85.7% (6/7), and the ratio of vegetables oil is 14.3% (1/7) to 50%.

2. the method for claim 1, the hydrogenation catalyst wherein in (1) step is conventional hydrogenation catalyst.

3. the method for claim 1, hydrogenation catalyst wherein in (1) step is Mo-Ni-P hydrogenation catalyst, wherein, in oxide dry basis, MoO3 accounts for the 19-30w% of total catalyst weight, NiO accounts for the 7-10w% of total catalyst weight, and P2O5 accounts for the 2-5w% of total catalyst weight, and all the other are amorphous silicic acid alumina supporter.

4. method as claimed in claim 1 or 2, the solvent wherein in (2) step be selected from furfural, sherwood oil, phenol, ether, tetramethylene sulfone, dimethyl sulfoxide (DMSO), dimethyl methyl phthalein amine or N monomethyl pyrrolidone one or more.

5. the method as described in claim 1 or 2 or 3, the solvent wherein in (2) step is furfural.