CN105694967A - Processing method for coal tar and high-octane-number gasoline prepared by using same - Google Patents
Processing method for coal tar and high-octane-number gasoline prepared by using same Download PDFInfo
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Abstract
The invention discloses a processing method for coal tar and high-octane-number gasoline prepared by using the same. The method comprises the following steps: (1) pretreating coal tar; (2) subjecting pretreated coal tar to distillation separation so as to obtain a phenol oil fraction and a heavy fraction; (3) subjecting the phenol oil fraction and alcohol to an etherification reaction; (4) subjecting the heavy fraction to hydrotreatment; and (5) blending a gasoline fraction obtained after hydrotreatment and a high-octane-number additive obtained after etherification of phenol oil so as to obtain high-octane-number gasoline. The processing method provided by the invention can prepare high-octane-number blended gasoline according with national standards, and overcomes the problem of pollution in conventional phenol removing method for phenol oil, the problem of hydrogen consumption in conventional hydrotreatment of phenol oil and the problem of a low octane number of gasoline prepared through hydrotreatment of coal tar.
Description
Technical field
The invention belongs to coal tar processing technology field, in particular it relates to the processing method of a kind of coal tar and the high-knock rating gasoline with the method acquisition。
Background technology
Coal tar is an important side-product in pyrolysis of coal distillation process process, it it is a kind of mixture forming complexity, difference according to pyrolysis of coal pyrolysis temperature and process approach, coal tar can be divided into coalite tar, medium temperature coal tar and high temperature coal-tar, and its composition difference is bigger。
At present, the course of processing of China's coal tar routine is to cut, through pretreatment distillation, the various fractions that component is several, adopt various fractions either physically or chemically to carry out (such as acid-alkali washing, distillation, polymerization, method for crystallising) processing again and extract various chemicals, also have and directly burn as thick replacement of fuel heavy oil greatly。Traditional processing method technique is more backward, separates and purifies difficulty relatively big, be not easily formed scale, can produce large amount of sewage, waste residue, contaminated environment simultaneously, further, since coal tar sulfur, nitrogen compound content are high, direct burning can produce substantial amounts of SOXAnd NOX, cause serious environmental pollution。Therefore, the clean processing of coal tar and effective utilization also become extremely important。
CN100590182C discloses a kind of coal tar hydrocracking technique, after coal tar elimination mechanical admixture and water, is separated into light ends and heavy end after hydrogenated refining reaction, separates, finally obtain gasoline, diesel oil and tail oil after the hydrogenated cracking of heavy end。
CN200810209558.5 discloses a kind of delay coking of coal tar and hydrogenation combined process, the method is the method that coal tar is adopted delayed coking and hydrogenation, carry out delayed coking, hydrogenation and after refine, hydrogenation includes hydrotreatment, hydrofinishing, hydrogenation cracking, finally obtains liquefied gas, fuel oil and lube base oil。
CN101885982A discloses the hydrogenation method for coal tar suspension bed of a kind of heterogeneous catalysis, the method includes coal tar raw material pretreatment and separated, coal tar heavy end floating bed hydrocracking and the light ends oil routine upgrading course of processing, wherein, the pretreatment of coal tar raw material is that coal tar raw material carries out conventional dehydration and elimination mechanical admixture, coal tar raw material separated be pretreated coal tar adopts the method for distillation be separated into less than 260 DEG C, 260～370 DEG C and more than 370 DEG C of three fractions。Adopt traditional coal tar dephenolization method less than 260 DEG C of fractions, carry out phenol removal, it is thus achieved that dephenolize oil and crude phenols；Hydrocracked, treated is carried out through suspension bed more than 370 DEG C of heavy distillates。260～370 DEG C of fractions are as the raw oil of upgrading processing fuel oil and industrial chemicals。
CN103450937A discloses a kind of method that coal tar produces low-coagulation diesel oil and liquid paraffin, the method is made up of following steps: the mild hydrogenation of coal tar carries out mild hydrogenation under molybdenum-nickel type catalyst effect in hydrogenation reactor after refining-coal tar and hydrogen being mixed and refines, and obtains hydrofinishing and generates oil；The fractional distillation of hydrogenation products-hydrofinishing generation oil is carried out fractional distillation in fractionating column, yields less than the naphtha cut of 180 DEG C, the diesel oil distillate of 180-360 DEG C and the residue fraction more than 360 DEG C；The urea complexation dewaxing of diesel oil distillate-isopropanol, carbamide and water are mixed urine, isolates low-coagulation diesel oil and urea complex；The decomposition of urea complex-decomposed in decomposition reactor by the urea complex obtained, obtains liquid paraffin。
But all there is with serious pollution problem in carbolic oil dephenolize process in existing technology, the hydrogen of carbolic oil hydrotreatment consumes problem, and coal tar hydrogenating processes and obtains the problem that octane number is low。
Summary of the invention
The invention aims to solve the problems referred to above of the prior art, and the processing method that a kind of new coal tar is provided。
To achieve these goals, the present invention provides the processing method of a kind of coal tar, and the method comprises the following steps:
(1) coal tar is carried out pretreatment；
(2) coal tar through pretreatment is carried out separated, be separated into carbolic oil fraction and heavy end；
(3) described carbolic oil fraction and alcohol are carried out etherification reaction；
(4) described heavy end is carried out hydrotreatment。
(5) by step 4) in the gasoline fraction that obtains of hydrotreatment and step 3) in the product that obtains of etherificate be in harmonious proportion and obtain high-octane gasoline。
Another aspect of the present invention provides a kind of high-knock rating gasoline obtained by the processing method of above-mentioned coal tar。
The present invention can pass through by coal tar pretreatment after mechanical removal impurity and water, through being distillated into carbolic oil fraction and heavy end, wherein, obtains product (such as, high-octane gasoline additive) after carbolic oil fraction and alcohol are carried out etherification reaction；By hydrogenated for heavy end refining reaction, hydrocracking reaction and generation hydrogasoline, hydrogenated diesel oil and hydrogenation tail oil after hydro-upgrading reaction；The recycling product that obtains of etherification reaction obtains the high-octane blended gasoline meeting GB being in harmonious proportion hydrogasoline, obtains product (such as, high 16 value diesel oil) after the hydrogenated upgrading of hydrogenated diesel oil。
Accompanying drawing explanation
Fig. 1 is the process chart of the coal tar processing method of a kind of detailed description of the invention according to the present invention；
Fig. 2 is the process chart of the coal tar processing method of the another kind of detailed description of the invention according to the present invention。
Description of reference numerals
1, pretreatment dehydration de-slag 2, separated
3, etherification reaction 4, hydrofinishing
5, hydrogenation cracking 6, fractional distillation
7, hydro-upgrading 8, be in harmonious proportion
Detailed description of the invention
Hereinafter the specific embodiment of the present invention is described in detail。It should be appreciated that detailed description of the invention described herein is merely to illustrate and explains the present invention, it is not limited to the present invention。
The processing method that the invention provides a kind of coal tar, the method comprises the following steps:
(1) coal tar is carried out pretreatment；
(2) coal tar through pretreatment is carried out separated, be separated into carbolic oil fraction and heavy end；
(3) described carbolic oil fraction and alcohol are carried out etherification reaction；
(4) described heavy end is carried out hydrotreatment；
(5) by step 4) in the gasoline fraction that obtains of hydrotreatment and step 3) in the product that obtains of etherificate be in harmonious proportion and obtain high-octane gasoline。
According to the present invention, described coal tar is not particularly limited, it is possible to for the conventional selection of this area, for instance, it is possible to generate one or more in oil for coalite tar, medium temperature coal tar, high temperature coal-tar or DCL/Direct coal liquefaction；In the present invention, it is preferred to, described coal tar is coalite tar and/or medium temperature coal tar。
According to the present invention, described distillation is not particularly limited, it is possible to conventional for this area selects, in the present invention, it is preferred to, described distillation is air-distillation or decompression distillation。
According to the present invention, described pretreatment can take off Slag treatment for dehydration, namely, this pretreatment is the process that coal tar raw material carries out conventional dehydration and elimination mechanical admixture, it addition, the mode of described pretreatment is not particularly limited, it is possible to for the conventional selection of those skilled in the art。
Preferably, in step (2), described in described separated process, the cutting temperature of carbolic oil fraction and described heavy end can be 190-220 DEG C。
According to the present invention, in described carbolic oil fraction, the total amount of phenol can be more than 20 weight %, it is preferable that in described carbolic oil fraction, the total amount of phenol is 50-70 weight %。
According to the present invention, in step (3), the mol ratio of the phenol in described carbolic oil fraction and described alcohol can be 1:1-5, it is preferred to 1:3-5。
According to the present invention, described alcohol is not particularly limited, it is possible to for the conventional selection of this area, in the present invention, described alcohol can be C1-C3Aliphatic alcohol in one or more；Preferably, described alcohol is one or more in methanol, ethanol and normal propyl alcohol；It is highly preferred that described alcohol is methanol and/or ethanol。It addition, when described alcohol is selected from C1-C3Aliphatic alcohol in two or more time, two or more selected alcohol consumption each other is not particularly limited, if total mole of two or more selected alcohol meet its of above-mentioned restriction with the scope of the mol ratio of the phenol in described carbolic oil fraction within。
Preferably, in step (3), the condition of described etherification reaction includes: temperature is 350-450 DEG C, and the mol ratio of phenol and alcohol is 1:1-5, and Mean fluid air speed is 0.5h-1-2h-1。
According to the present invention, described etherification reaction preferably carries out in the presence of a catalyst, and described catalyst is not particularly limited, it is possible to for the conventional selection of this area, described catalyst can be Al2O3、Al2O3-SiO2One or more in composite oxides, solid supported acid catalyst and solid supported base catalyst。
In accordance with the present invention it is preferred that, in step (4), described hydrotreatment carries out fractional distillation to obtain hydrogasoline, hydrogenated diesel oil and hydrogenation tail oil after including hydrofinishing。The condition of described hydrofining reaction includes: reaction temperature can be 350-400 DEG C, and pressure can be 8-20Mpa, and hydrogen to oil volume ratio can be 800-2000:1, and Mean fluid air speed can be 0.5h-1-3h-1。
According to the present invention, described hydrofining reaction preferably carries out in the presence of a catalyst, described catalyst is not particularly limited, it can be the conventional selection of this area, described catalyst is conventional Hydrobon catalyst, and mainly with vib and group VIII metal for active component, vib metals is generally Mo and/or W, group VIII metal Co and/or Ni, with silicon-containing alumina or aluminium oxide for carrier。
In accordance with the present invention it is preferred that, the blending weight ratio of described hydrogasoline and described etherification reaction product can be 0.3-7.0:1。
According to the present invention, described hydrotreating method can also include: hydrogenated diesel oil carries out hydro-upgrading to obtain upgrading diesel oil。
According to the present invention, the condition of described hydro-upgrading reaction includes: reaction temperature can be 300-400 DEG C, and pressure can be 8-20Mpa, hydrogen to oil volume ratio can for 500-2000:1, and Mean fluid air speed can be 0.5h-1-3h-1。
According to the present invention, the reaction of described hydro-upgrading preferably carries out in the presence of a catalyst, described catalyst is not particularly limited, it can be the conventional selection of this area, described catalyst is have higher selectivity of ring-opening and the saturated catalyst of good aromatic hydrocarbons, and mainly with vib and group VIII metal for active component, vib metals is generally Mo and/or W, group VIII metal Co and/or Ni, with salic, silicon-containing alumina and molecular sieve for carrier。
In accordance with the present invention it is preferred that, described hydrotreating method can also include: hydrogenation tail oil carries out hydrogenation cracking to obtain cracked oil, and makes the described cracked oil of part return unifining process, carries out hydrofinishing together with described heavy end；Or make the described cracked oil of part return the fractional distillation process of hydrofinishing products therefrom, carry out fractional distillation together with hydrofinishing products therefrom。
According to the present invention, preferably, described hydrotreating method can also include: hydrogenation tail oil carries out hydrogenation cracking to obtain cracked oil, this cracked oil is carried out fractional distillation to obtain hydrogenation cracking gasoline, hydrogenation cracked diesel oil and cracking tail oil, and described cracking tail oil is returned hydrocracking process, carry out hydrogenation cracking together with described hydrogenation tail oil。
Preferably, in step (4), described hydrotreatment also includes: by described hydrogenation cracking gasoline and step 3) in the product that obtains of etherificate be in harmonious proportion and obtain high-octane gasoline。
According to the present invention, the condition of described hydrogenation cracking includes: answer temperature can be 360-400 DEG C, and pressure can be 8-20Mpa, hydrogen to oil volume ratio can for 800-2000:1, and Mean fluid air speed can be 0.5h-1-3h-1。
According to the present invention, the reaction of described hydro-upgrading preferably carries out in the presence of a catalyst, described catalyst is not particularly limited, it can be the conventional selection of this area, hydrocracking process used catalyst is conventional hydrocracking catalyst, mainly with vib and group VIII metal for active component, with amorphous silicon aluminium and molecular sieve for carrier, vib metals is generally Mo and/or W, group VIII metal Co and/or Ni。
Specifically, the processing method according to the coal tar of another embodiment of the invention, as it is shown in figure 1, the method comprises the following steps:
(1) by de-for preprocessed for coal tar dehydration slag 1；
(2) coal tar through pretreatment is carried out separated 2, be separated into carbolic oil fraction and heavy end；
(3) described carbolic oil fraction and alcohol are carried out etherification reaction 3, obtain etherification product (high-octane rating additive)；
(4) described heavy end being carried out hydrofinishing 4, fractional distillation obtains hydrogasoline, hydrogenated diesel oil and hydrogenation tail oil；
(5) the described hydrogenation tail oil the obtained circulation in step (4) is carried out hydrogenation cracking 5 again to obtain cracked oil, the described cracked oil of part is made to return fractional distillation 6 process of hydrofinishing 4 products therefrom, fractional distillation 6 is carried out, it is thus achieved that hydrogasoline, hydrogenated diesel oil and hydrogenation tail oil (this hydrogenation tail oil again circulates and carries out hydrogenation cracking) together with hydrofinishing 4 products therefrom；
(6) the described hydrogasoline obtained being in harmonious proportion in 8 steps (4) with the etherification reaction product (described high-octane rating additive) obtained in step (3), it is thus achieved that blended gasoline；
(7) the described hydrogenated diesel oil obtained in step (3) and the hydrogenated upgrading 7 of hydrogenated diesel oil obtained in step (5) are obtained upgrading diesel oil。
Specifically, the processing method according to the coal tar of another embodiment of the invention, as in figure 2 it is shown, the method comprises the following steps:
(1) by de-for preprocessed for coal tar dehydration slag 1；
(2) coal tar through pretreatment is carried out separated 2, be separated into carbolic oil fraction and heavy end；
(3) described carbolic oil fraction and the etherified reaction 3 of alcohol are obtained etherification product (high-octane rating additive)；
(4) described heavy end is carried out hydrofinishing 4, be fractionated into 6 and obtain hydrogasoline, hydrogenated diesel oil and hydrogenation tail oil；
(5) the described hydrogenation tail oil the obtained circulation in step (4) is reacted to obtain cracked oil then through hydrogenation cracking 5, this cracked oil is carried out fractional distillation 6 to obtain hydrogenation cracking gasoline, hydrogenation cracked diesel oil and cracking tail oil, and described cracking tail oil is returned hydrogenation cracking 5 process, carry out hydrogenation cracking 5 together with described hydrogenation tail oil, and constantly circulate；
(6) the described hydrogenation cracking gasoline obtained being in harmonious proportion in step (4) described hydrogasoline and step (5) with the etherification product (described high-octane rating additive) obtained in step (3), it is thus achieved that blended gasoline；
(7) the described hydrogenated diesel oil obtained in step (3) and the hydrogenated upgrading 7 of hydrogenation cracked diesel oil obtained in step (5) are obtained upgrading diesel oil。
In a word, the present invention passes through coal tar pretreatment after mechanical removal impurity and water, is carbolic oil fraction and heavy end through separated, wherein, obtains high-octane gasoline additive after etherified for carbolic oil fraction reaction；By hydrogenated for heavy end refining reaction, hydrocracking reaction and generation hydrogasoline and hydrogenated diesel oil after hydro-upgrading reaction；Recycling etherificate obtains high octane additive and obtains and meet high-octane blended gasoline of GB being in harmonious proportion hydrogasoline, obtains high 16 value diesel oil after the hydrogenated upgrading of hydrogenated diesel oil。
Hereinafter will be described the present invention by embodiment。
In following example, gasoline products and diesel product property testing method are with reference to motor petrol GB17930-201 and derv fuel GB19147-2009。
The percentage by volume of contained isobutyltrimethylmethane. in ideal fuels when octane number is numerically equal to identical with sample anti-knock properties under prescribed conditions。
Gasoline mixed oil refers to and adds some additives in the oil, reconciles into the GB gasoline met the requirements of the customers。
Embodiment 1
After preprocessed for Shenmu County's medium temperature coal tar elimination mechanical admixture and water, being through air-distillation by the coal tar through pretreatment at 200 DEG C in temperature, fractionate out carbolic oil fraction and heavy end, wherein, in described carbolic oil fraction, the total amount of phenol is 60 weight %；Again by phenol in this carbolic oil fraction and methanol with mol ratio for 1:5, it is at 450 DEG C in temperature, liquid air speed 1.5h-1, at catalyst Al2O3Existence under carry out etherification reaction, result obtains high-octane gasoline additive, and its octane number is 111.9；
By described heavy end under the existence of Hydrobon catalyst, reaction temperature be 380 DEG C, pressure be 12Mpa, hydrogen to oil volume ratio be 2000:1, Mean fluid air speed is 1h-1Under carry out hydrofining reaction, fractional distillation obtains hydrogasoline, hydrogenated diesel oil and hydrogenation tail oil；
As it is shown in figure 1, by this hydrogenation tail oil through circulation again reaction temperature be 400 DEG C, pressure be 12Mpa, hydrogen to oil volume ratio be 1500:1, Mean fluid air speed is 0.8h-1Under carry out hydrocracking reaction and obtain cracked oil, and make the described cracked oil of part return unifining process, carry out hydrofinishing together with described heavy end, then through fractional distillation, it is thus achieved that hydrogasoline, hydrogenated diesel oil and hydrogenation tail oil；
Then, by hydrogenated diesel oil reaction temperature be 380 DEG C, pressure be 12Mpa, hydrogen to oil volume ratio be 1200:1, Mean fluid air speed is 0.5h-1Under carry out hydro-upgrading, it is thus achieved that upgrading diesel oil-Gao 16 is worth diesel oil；
Then, again by hydrogasoline above-mentioned for the mediation of the etherified product being obtained by reacting high-octane gasoline additive, wherein, the beakeven weight of hydrogasoline and high-octane gasoline additive described in the etherified product being obtained by reacting is than for 2.8:1, it is thus achieved that blended gasoline-high-octane gasoline。
After tested, the composition of high-octane gasoline and high 16 value diesel oil, gasoline products character is as shown in table 1, diesel product character and shown in table 2。
Table 1
Note: No. 93 GB parameters are No. 93 motor petrol canonical parameters of GB17930 2011 " motor petrol "
Table 2
Note: No. 0 GB parameter is No. 0 derv fuel canonical parameter of GB19147 2009 " derv fuel "
Embodiment 2
After preprocessed for Shenmu County's medium temperature coal tar elimination mechanical admixture and water, being through air-distillation by the coal tar through pretreatment at 200 DEG C in temperature, fractionate out carbolic oil fraction and heavy end, wherein, in described carbolic oil fraction, the total amount of phenol is 60 weight %；It is 350 DEG C at mol ratio for 1:5 in temperature by phenol in this carbolic oil fraction and methanol again, liquid air speed 0.5h-1, at catalyst Al2O3Existence under carry out etherification reaction, result obtains high-octane gasoline additive, and its octane number is 109.1；
By described heavy end under the existence of Hydrobon catalyst, reaction temperature be 360 DEG C, pressure be 20Mpa, hydrogen to oil volume ratio be 1000:1, Mean fluid air speed is 2h-1Under carry out hydrofining reaction, fractional distillation obtains hydrogasoline, hydrogenated diesel oil and hydrogenation tail oil；
As it is shown in figure 1, by this hydrogenation tail oil through circulation again reaction temperature be 430 DEG C, pressure be 20Mpa, hydrogen to oil volume ratio be 1200:1, Mean fluid air speed is 1.2h-1Under carry out hydrocracking reaction and obtain cracked oil, and make the described cracked oil of part return unifining process, carry out hydrofinishing together with described heavy end, then through fractional distillation, it is thus achieved that hydrogasoline, hydrogenated diesel oil and hydrogenation tail oil；
Then, by hydrogenated diesel oil reaction temperature be 400 DEG C, pressure be 20Mpa, hydrogen to oil volume ratio be 1200:1, Mean fluid air speed is 1.6h-1Under carry out hydro-upgrading, it is thus achieved that upgrading diesel oil-Gao 16 is worth diesel oil；
Then, again by hydrogasoline above-mentioned for the mediation of the etherified product being obtained by reacting high-octane gasoline additive, wherein, the beakeven weight of hydrogasoline and high-octane gasoline additive described in the etherified product being obtained by reacting is than for 2.2:1, it is thus achieved that blended gasoline-high-octane gasoline。
After tested, the composition of high-octane gasoline and high 16 value diesel oil, gasoline products character is as shown in table 3, and diesel product character is as indicated at 4。
Table 3
Note: No. 93 GB parameters are No. 93 motor petrol canonical parameters of GB17930 2011 " motor petrol "
Table 4
Note: No. 0 GB parameter is No. 0 derv fuel canonical parameter of GB19147 2009 " derv fuel "
Embodiment 3
After preprocessed for Shenmu County's medium temperature coal tar elimination mechanical admixture and water, being through air-distillation by the coal tar through pretreatment at 200 DEG C in temperature, fractionate out carbolic oil fraction and heavy end, wherein, in described carbolic oil fraction, the total amount of phenol is 60 weight %；It is 400 DEG C at mol ratio for 1:3 in temperature by phenol in this carbolic oil fraction and methanol again, liquid air speed 0.5h-1, at catalyst Al2O3Existence under carry out etherification reaction, result obtains high-octane gasoline additive, and its octane number is 120.5；By described heavy end under the existence of Hydrobon catalyst, reaction temperature be 380 DEG C, pressure be 12Mpa, hydrogen to oil volume ratio be 2000:1, Mean fluid air speed is 1h-1Under carry out hydrofining reaction, fractional distillation obtains hydrogasoline, hydrogenated diesel oil and hydrogenation tail oil；
As it is shown in figure 1, by this hydrogenation tail oil through circulation again reaction temperature be 400 DEG C, pressure be 12Mpa, hydrogen to oil volume ratio be 1500:1, Mean fluid air speed is 0.8h-1Under carry out hydrocracking reaction and obtain cracked oil, and make the described cracked oil of part return unifining process, carry out hydrofinishing together with described heavy end, then through fractional distillation, it is thus achieved that hydrogasoline, hydrogenated diesel oil and hydrogenation tail oil；
Then, by hydrogenated diesel oil reaction temperature be 380 DEG C, pressure be 12Mpa, hydrogen to oil volume ratio be 2000:1, Mean fluid air speed is 1.5h-1Under carry out hydro-upgrading, it is thus achieved that upgrading diesel oil-Gao 16 is worth diesel oil；
Then, again by hydrogasoline above-mentioned for the mediation of the etherified product being obtained by reacting high-octane gasoline additive, wherein, the beakeven weight of hydrogasoline and high-octane gasoline additive described in the etherified product being obtained by reacting is than for 7.0:1, it is thus achieved that blended gasoline-high-octane gasoline。
After tested, the composition of high-octane gasoline and high 16 value diesel oil, gasoline products character is as shown in table 1, and diesel product character is as shown in table 6。
Table 5
Note: No. 93 GB parameters are No. 93 motor petrol canonical parameters of GB17930 2011 " motor petrol "
Table 6
Note: No. 0 GB parameter is No. 0 derv fuel canonical parameter of GB19147 2009 " derv fuel "
Embodiment 4
By coalite tar in Shenmu County after mechanical pretreatment imurity-removal and water, through being through air-distillation through the coal tar of pretreatment at 200 DEG C in temperature, fractionating out carbolic oil fraction and heavy end, wherein, in described carbolic oil fraction, the total amount of phenol is 60 weight %；It is 450 DEG C at liquid air speed 0.5h with mol ratio for 1:1 in temperature by described carbolic oil fraction and methanol again-1, at catalyst Al2O3-SiO2Carrying out etherification reaction under the existence of composite oxides, result obtains high-octane gasoline additive 97.1；
By described heavy end under the existence of Hydrobon catalyst, reaction temperature be 380 DEG C, pressure be 12Mpa, hydrogen to oil volume ratio be 1500:1, Mean fluid air speed is 1.0h-1Under carry out hydrofining reaction, fractional distillation obtains hydrogasoline, hydrogenated diesel oil and hydrogenation tail oil；
As it is shown in figure 1, by this hydrogenation tail oil through circulation again reaction temperature be 390 DEG C, pressure be 12Mpa, hydrogen to oil volume ratio be 1500:1, Mean fluid air speed is 1.6h-1Under carry out hydrocracking reaction and obtain cracked oil, and make the described cracked oil of part return unifining process, carry out hydrofinishing together with described heavy end, then through fractional distillation, it is thus achieved that hydrogasoline, hydrogenated diesel oil and hydrogenation tail oil；
Then, by hydrogenated diesel oil reaction temperature be 360 DEG C, pressure be 12Mpa, hydrogen to oil volume ratio be 1200:1, Mean fluid air speed is 1.2h-1Under carry out hydro-upgrading and obtain upgrading diesel oil-Gao 16 value diesel oil；
Then, again by the etherified product being obtained by reacting high-octane gasoline additive above-mentioned hydrogasoline of mediation, wherein, the beakeven weight of hydrogasoline and high-octane gasoline additive described in the etherified product being obtained by reacting is than for 0.3:1, it is thus achieved that blended gasoline-high-octane gasoline。
After tested, the composition of high-octane gasoline and high 16 value diesel oil, gasoline products character is as shown in table 7, and diesel product character is as shown in table 8。
Table 7
Note: No. 93 GB parameters are No. 93 motor petrol canonical parameters of GB17930 2011 " motor petrol "
Table 8
Note: No. 0 GB parameter is No. 0 derv fuel canonical parameter of GB19147 2009 " derv fuel "
Embodiment 5
According to the method identical with embodiment 3, coal tar being processed, be different in that, the hydroprocessing processes of heavy end adopts double; two fractionating column technique and flow chart 2。
By described heavy end under the existence of Hydrobon catalyst, reaction temperature be 380 DEG C, pressure be 12Mpa, hydrogen to oil volume ratio be 2000:1, Mean fluid air speed is 1h-1Under carry out hydrofining reaction, fractional distillation obtains hydrogasoline, hydrogenated diesel oil and hydrogenation tail oil；
As in figure 2 it is shown, by this hydrogenation tail oil through circulation again reaction temperature be 400 DEG C, pressure be 12Mpa, hydrogen to oil volume ratio be 1500:1, Mean fluid air speed is 0.8h-1Under carry out hydrocracking reaction and obtain cracked oil, this cracked oil is carried out fractional distillation to obtain hydrogenation cracking gasoline, hydrogenation cracked diesel oil and hydrocracking tail oil, and described cracking tail oil is returned hydrocracking process, carry out hydrogenation cracking together with described hydrogenation tail oil；Then, by hydrogenated diesel oil and hydrogenation cracked diesel oil reaction temperature be 380 DEG C, pressure be 12Mpa, hydrogen to oil volume ratio be 2000:1, Mean fluid air speed is 1.5h-1Under carry out hydro-upgrading, it is thus achieved that upgrading diesel oil-Gao 16 is worth diesel oil；
Then, again the etherified high-octane gasoline additive of the product being obtained by reacting it is in harmonious proportion above-mentioned hydrogasoline and is hydrogenated with cracking gasoline, wherein, the beakeven weight of hydrogasoline and hydrogenation cracking gasoline and high-octane gasoline additive described in the etherified product being obtained by reacting ratio is for 7.0:1, obtain blended gasoline-high-octane gasoline, gasoline products character is as shown in table 9, and diesel product character is as shown in table 10。
Table 9
Note: No. 93 GB parameters are No. 93 motor petrol canonical parameters of GB17930 2011 " motor petrol "
Table 10
Note: No. 0 GB parameter is No. 0 derv fuel canonical parameter of GB19147 2009 " derv fuel "
Embodiment 6
According to the method identical with embodiment 3, coal tar being processed and carbolic oil etherification reaction, condition is different in that, the reaction temperature of hydrofining reaction is 400 DEG C, reaction pressure is 12MPa, hydrogen to oil volume ratio is 800:1, and Mean fluid air speed is 3h-1Under carry out hydrofining reaction, fractional distillation obtains hydrogasoline, hydrogenated diesel oil and hydrogenation tail oil；Hydrogenation tail oil reaction temperature be 370 DEG C, reaction pressure be 12MPa, hydrogen to oil volume ratio be 2000:1, Mean fluid air speed is 0.5h-1Under carry out hydrocracking reaction；
Hydrogenated diesel oil reaction temperature be 400 DEG C, pressure be 12Mpa, hydrogen to oil volume ratio be 1200:1, Mean fluid air speed is 2h-1Under carry out hydro-upgrading, it is thus achieved that upgrading diesel oil-Gao 16 is worth diesel oil；
Then, again by the etherified product being obtained by reacting high-octane gasoline additive above-mentioned hydrogasoline of mediation, wherein, the beakeven weight of hydrogasoline and high-octane gasoline additive described in the etherified product being obtained by reacting is than for 6.1:1, it is thus achieved that blended gasoline-high-octane gasoline。
After tested, the composition of high-octane gasoline and high 16 value diesel oil, gasoline products character is as shown in table 11, and diesel product character is as shown in table 12。
Table 11
Note: No. 93 GB parameters are No. 93 motor petrol canonical parameters of GB17930 2011 " motor petrol "
Table 12
Note: No. 0 GB parameter is No. 0 derv fuel canonical parameter of GB19147 2009 " derv fuel "
Embodiment 7
According to the method identical with embodiment 3, coal tar being processed and carbolic oil etherification reaction, condition is different in that, the reaction temperature of hydrofining reaction is 350 DEG C, reaction pressure is 12MPa, hydrogen to oil volume ratio is 2000:1, and Mean fluid air speed is 1.2h-1Under carry out hydrofining reaction, fractional distillation obtains hydrogasoline, hydrogenated diesel oil and hydrogenation tail oil；Hydrogenation tail oil reaction temperature be 430 DEG C, reaction pressure be 12MPa, hydrogen to oil volume ratio be 500:1, Mean fluid air speed is 3h-1Under carry out hydrocracking reaction；
Hydrogenated diesel oil reaction temperature be 370 DEG C, pressure be 20Mpa, hydrogen to oil volume ratio be 800:1, Mean fluid air speed is 3h-1Under carry out hydro-upgrading, it is thus achieved that upgrading diesel oil-Gao 16 is worth diesel oil；
Then, again by the etherified product being obtained by reacting high-octane gasoline additive above-mentioned hydrogasoline of mediation, wherein, the beakeven weight of hydrogasoline and high-octane gasoline additive described in the etherified product being obtained by reacting is than for 5.5:1, it is thus achieved that blended gasoline-high-octane gasoline。
After tested, the composition of high-octane gasoline and high 16 value diesel oil, gasoline products character is as shown in table 13, and diesel product character is as shown in table 14。
Table 13
Note: No. 93 GB parameters are No. 93 motor petrol canonical parameters of GB17930 2011 " motor petrol "
Table 14
Note: No. 0 GB parameter is No. 0 derv fuel canonical parameter of GB19147 2009 " derv fuel "
Embodiment 8
According to the method identical with embodiment 3, coal tar being processed and carbolic oil etherification reaction, condition is different in that, the reaction temperature of hydrofining reaction is 370 DEG C, hydrogen to oil volume ratio is 2000:1, reaction pressure 8MPa, Mean fluid air speed are 0.5h-1Under carry out hydrofining reaction, fractional distillation obtains hydrogasoline, hydrogenated diesel oil and hydrogenation tail oil；Hydrogenation tail oil reaction temperature be 400 DEG C, hydrogen to oil volume ratio be 1500:1, reaction pressure 8MPa, Mean fluid air speed be 1h-1Under carry out hydrocracking reaction；
Hydrogenated diesel oil reaction temperature be 360 DEG C, pressure be 8Mpa, hydrogen to oil volume ratio be 200:1, Mean fluid air speed is 0.8h-1Under carry out hydro-upgrading, it is thus achieved that upgrading diesel oil-Gao 16 is worth diesel oil；
Then, again by the etherified product being obtained by reacting high-octane gasoline additive above-mentioned hydrogasoline of mediation, wherein, the beakeven weight of hydrogasoline and high-octane gasoline additive described in the etherified product being obtained by reacting is than for 4.1:1, it is thus achieved that blended gasoline-high-octane gasoline。
After tested, the composition of high-octane gasoline and high 16 value diesel oil, gasoline products character such as table 15, diesel product character is as shown in table 16。
Table 15
Note: No. 93 GB parameters are No. 93 motor petrol canonical parameters of GB17930 2011 " motor petrol "
Table 16
Note: No. 0 GB parameter is No. 0 derv fuel canonical parameter of GB19147 2009 " derv fuel "
Visible according to embodiment 1-8 and table 1-16, adopt the present invention method, by by coal tar pretreatment after mechanical removal impurity and water, through being distillated into carbolic oil fraction and heavy end, wherein, after etherified for carbolic oil fraction reaction, high-octane gasoline additive is obtained；By hydrogenated for heavy end refining reaction, hydrocracking reaction and generation hydrogasoline and hydrogenated diesel oil after hydro-upgrading reaction；Recycling etherificate obtains high octane additive and obtains and meet high-octane blended gasoline of GB being in harmonious proportion hydrogasoline, obtains high 16 value diesel oil after the hydrogenated upgrading of hydrogenated diesel oil。Not only solve the hydrogen consumption problem of pollution problem and carbolic oil hydrotreatment in existing carbolic oil dephenolization method, and coal tar hydrogenating processes and obtains the problem that octane number is low, and be obtained in that the gasoline meeting GB。
The preferred embodiment of the present invention described in detail above, but, the present invention is not limited to the detail in above-mentioned embodiment, it is possible to technical scheme is carried out multiple simple variant。
It is further to note that, each concrete technical characteristic described in above-mentioned detailed description of the invention, in reconcilable situation, it is possible to be combined by any suitable mode, in order to avoid unnecessary repetition, various possible compound modes are no longer illustrated by the present invention separately。
Additionally, can also carry out combination in any between the various different embodiment of the present invention, as long as it is without prejudice to the thought of the present invention, it should be considered as content disclosed in this invention equally。
Claims (18)
1. a processing method for coal tar, the method comprises the following steps:
(1) coal tar is carried out pretreatment；
(2) coal tar through pretreatment is carried out separated, be separated into carbolic oil fraction and heavy end；
(3) described carbolic oil fraction and alcohol are carried out etherification reaction；
(4) described heavy end is carried out hydrotreatment；
(5) by step 4) in the gasoline fraction that obtains of hydrotreatment and step 3) in the product that obtains of etherificate be in harmonious proportion and obtain high-octane gasoline。
2. method according to claim 1, wherein, in step (1), described pretreatment is the de-Slag treatment of dehydration。
3. method according to claim 1, wherein, in step (2), the cutting temperature that described separated process adopts is 190-220 DEG C。
4. method according to claim 1, wherein, in step (2), in described carbolic oil fraction, the content of phenol is more than 20 weight %。
5. the method according to any one of claim 1-4, wherein, in step (3), the mol ratio of the phenol in described carbolic oil fraction and described alcohol is 1:1-5。
6. the method according to any one of claim 1-5, wherein, in step (3), described alcohol is C1-C3Fatty alcohol in one or more。
7. method according to claim 1, wherein, in step (3), the condition of described etherification reaction includes: temperature is 350-450 DEG C, and Mean fluid air speed is 0.5h-1-2h-1。
8. the method according to any one of claim 1-7, wherein, in step (4), described hydrotreatment carries out fractional distillation to obtain hydrogasoline, hydrogenated diesel oil and hydrogenation tail oil after including hydrofinishing。
9. method according to claim 8, wherein, the condition of described hydrofining reaction includes: reaction temperature is 350-400 DEG C, and pressure is 8-20Mpa, and hydrogen to oil volume ratio is 800-2000:1, and Mean fluid air speed is 0.5h-1-3h-1。
10. the method according to any one of claim 1-9, in step (4), the blending weight ratio of described gasoline fraction and described etherification reaction product is 0.3-7:1。
11. method according to claim 8, wherein, in step (4), described hydrotreatment also includes: hydrogenated diesel oil carries out hydro-upgrading to obtain upgrading diesel oil。
12. method according to claim 11, wherein, the condition of described hydro-upgrading reaction includes: reaction temperature is 360-400 DEG C, and pressure is 8-20Mpa, hydrogen to oil volume ratio is 800-2000:1, and Mean fluid air speed is 0.5h-1-3h-1。
13. the method according to any one of-12 according to Claim 8, wherein, in step (4), described hydrotreatment also includes: hydrogenation tail oil carries out hydrogenation cracking to obtain cracked oil, and make at least part of described cracked oil return unifining process, carry out hydrofinishing together with described heavy end；Or make at least part of described cracked oil return the fractional distillation process of hydrofinishing products therefrom, carry out fractional distillation together with hydrofinishing products therefrom。
14. the method according to any one of-12 according to Claim 8, wherein, in step (4), described hydrotreatment also includes: hydrogenation tail oil carries out hydrogenation cracking to obtain cracked oil, this cracked oil is carried out fractional distillation to obtain hydrogenation cracking gasoline, hydrogenation cracked diesel oil and cracking tail oil, and described cracking tail oil is returned hydrocracking process, carry out hydrogenation cracking together with described hydrogenation tail oil。
15. the method according to claim 13 or 14, wherein, the condition of described hydrogenation cracking includes: temperature can be 370-430 DEG C, and pressure can be 8-20Mpa, and hydrogen to oil volume ratio can be 800-2000:1, and Mean fluid air speed can be 0.5h-1-3h-1。
16. the method according to claims 14 or 15, wherein, in step (4), described hydrotreatment also includes: by described hydrogenation cracking gasoline and step 3) in the product that obtains of etherificate be in harmonious proportion and obtain high-octane gasoline。
17. method according to claim 1, wherein, described coal tar is one or more in coalite tar, medium temperature coal tar, high temperature coal-tar or DCL/Direct coal liquefaction generation oil。
18. the high-knock rating gasoline that the processing method of the coal tar according to any one of claim 1-17 obtains。
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| CN115505417A (en) * | 2022-09-20 | 2022-12-23 | 西安交通大学 | Pretreatment solvent for medium and low temperature coal tar, and preparation method and application thereof |
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