CN105985221A - Method for preparing ethylene glycol by using raw material gas obtained through supplementing coke-oven gas to coke gasified gas - Google Patents
Method for preparing ethylene glycol by using raw material gas obtained through supplementing coke-oven gas to coke gasified gas Download PDFInfo
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- CN105985221A CN105985221A CN201510052532.4A CN201510052532A CN105985221A CN 105985221 A CN105985221 A CN 105985221A CN 201510052532 A CN201510052532 A CN 201510052532A CN 105985221 A CN105985221 A CN 105985221A
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Abstract
The invention discloses a method for preparing ethylene glycol by using raw material gas obtained through supplementing coke-oven gas to coke gasified gas. The method comprises the steps: (a) coking coal so as to obtain coke and the coke-oven gas; (b) carrying out purifying treatment on the coke-oven gas obtained in the step (a) so as to obtain first purified gas; (c) gasifying the coke obtained in the step (a) so as to obtain the coke gasified gas; (d) carrying out purifying treatment on the coke gasified gas obtained in the step (c) so as to obtain second purified gas; and (e) mixing the first purified gas and the second purified gas, and preparing the ethylene glycol by using the raw material gas obtained through mixing. According to the method disclosed by the invention, a novel coke utilization way of think is provided, and the coke-oven gas and the coke gasified gas are mixed and are further used for preparing the ethylene glycol in accordance with the characteristics that the content of hydrogen gas in the coke-oven gas is relatively high and the content of carbon monoxide in the coke gasified gas is relatively high, so that the economic benefit is obvious, the method has a significant significance in coking industry of our country, the influence and constraints on coke industry caused by steel industry are avoided, and the development of the coke industry is promoted.
Description
Technical field
The invention belongs to coal chemical technology, be specifically related to one with coal for raw material by coking and coke
Coke-stove gas is utilized to supplement the method that coke gas gained unstripped gas prepares ethylene glycol after gasification.
Background technology
Since the nineties, ethylene glycol (EG) demand of China increases year by year, but the degree of self-sufficiency one
The most on a declining curve, the current degree of self-sufficiency is still less than 30%, and therefore, ethylene glycol produces to be had extensively at home
General market.Traditional ethylene glycol synthetic route mainly has petroleum path and coal route, wherein, stone
Oil circuit line is oil ethylene, ethylene preparing ethylene glycol, and it is relatively costly；Coal route is that coal is direct
Vaporizing system synthesis gas, synthesis gas preparing ethylene glycol, wherein, coal gasification mainly has dry pulverized coal gas
Changing and coal water slurry gasification, coal itself is all had higher requirements by both, and due in synthesis gas one
Content of carbon oxide is higher, in addition it is also necessary to further transformed workshop section processes, to regulate C/Hratio, and ability
For synthesizing glycol, waste time and energy.
Further, since China's steel industry presently, there are serious production capacity surplus, so that coke
There is problem of excess production capacity accordingly in industry, even after enormous investment, part production capacity can only leave unused,
Waste, causes the situation that coke appearance of enterprise generally loses, and how to break away from steel industry STRENGTH ON COKE enterprise
The impact of industry and constraint, be the problem of current coke enterprise urgent need reply.
Summary of the invention
It is an object of the invention to provide one utilizes coke-stove gas to supplement coke gas gained unstripped gas
The method preparing ethylene glycol, with the problem solving current coke production capacity surplus.
For achieving the above object, the present invention is by the following technical solutions:
A kind of coke-stove gas is utilized to supplement the method that coke gas gained unstripped gas prepares ethylene glycol, institute
The method of stating includes:
A, utilize coal coking, obtain coke and coke-stove gas；
B, the coke-stove gas obtaining step a carry out purified treatment, obtain the first purification gas；
C, the coke obtaining step a gasify, and obtain coke gas；
D, the coke gas obtaining step c carry out purified treatment, obtain the second purification gas；
E, by described first purify gas and second purify gas mixing, and utilize mixing gained unstripped gas system
Standby ethylene glycol.
The method according to the invention, the coking described in step a is well known in the art to utilize coal
Produce the process of coke, such as, utilize feed coal to carry out coal-blending coking, obtain coke and coke-stove gas,
Said process is known in the art, repeats no more here.
The method according to the invention, the coke-stove gas in step b obtained step a is carried out at purification
Reason, obtains the first purification gas, and the decontamination process of described coke-stove gas is for it is known in the art that example
As included dedusting, tar separation, eluting benzene, thick desulfurization, fine de-sulfur and methane conversion etc.；Wherein,
The purpose of tar separation is to reclaim the tar in coke-stove gas, and tar is important industrial chemicals,
Containing multiple macromolecular compound (such as aromatic compound), there is higher economic worth,
In the present invention, described tar separation can use separating tar from coke-stove gas commonly used in the art
Method, such as sprayed by ammonia or electric trapper tar device separating tar from coke-stove gas, coal
In gas, remaining a small amount of tar can remove further with activated carbon adsorption.Eluting benzene is to remove
Remove the benzene in oven gas, coke-stove gas utilizes washing oil to remove containing a small amount of benzene, removing
Benzene can be as crude benzol product, and crude benzol is also important industrial chemicals, it may have higher economic worth.
In the present invention, coke oven gas desulfurization is the conventional process of this area coke oven gas purification, uses
In the sulfur content reduced in coke-stove gas, such as dry desulfurization and wet desulphurization, wet desulphurization is also named
Solwution method desulfurization, makes again thick desulfurization can reclaim most sulfur in oven gas, thus produces sulfur
Product, dry desulfurization is further desulfurization, so referred to as fine de-sulfur, its sulfur method is this area
Known, repeat no more here.In the present invention, the purpose that described methane converts is by portion
Divide oxidation that the methane in coke-stove gas is converted into effective ingredient (CO and H2), its method is ability
Known to territory, repeat no more here.
The method according to the invention, the coke in step c obtained step a gasifies, and obtains
Coke gas；Preferably, in step c, the amount of coke for coke gas is burnt in step a
0.3-0.4 times of carbon yield；More preferably 0.33-0.37 times；Further it is preferably 0.34-0.36
Times, so that carbon monoxide is about 1:2 with the volume ratio of hydrogen in described unstripped gas, such as 1:1.9～2.1,
Improve the utilization rate of available gas in unstrpped gas.
In the art, when coal product is carried out gasification process, fluid bed, gas can be used
Change bed etc. to gasify.In the present invention, in the face of the gasification needs of coke product prepared by step a,
Research and develop through for many years, thus propose following preferably coke gasification technique, i.e. in step c,
When STRENGTH ON COKE gasifies, with steam and oxygen as gasifying agent, fixed bed STRENGTH ON COKE is utilized to carry out
Gasification, vapor pressure be 0.09～0.11MPa pressure, gasification temperature be 1100～1300 DEG C, gasification
It is 6～50mm coke buttons with coke；Preferably, the consumption of described steam is 1.7～2.0 ton/ton Jiao
Charcoal, the consumption of described oxygen is 460～500Nm3/ ton coke；It is further preferred that described gasification
Pressure is normal pressure, and gasification temperature is 1150～1250 DEG C, and the consumption of described steam is 1.8～1.9
Ton/ton coke, the consumption of described oxygen is 475～485N m3/ ton coke, promotes gasification with further
Effect, obtains suitable C/Hratio, follow-up mixing.
The method according to the invention, the coke gas in step d obtained step c is carried out at purification
Reason, obtains the second purification gas；The decontamination process of described coke oven gas is for it is known in the art that example
As included dedusting, tar separation, eluting benzene and desulfurization etc., with coke-stove gas or coal direct gasification
Gained coal gas is compared, and it will be understood by those skilled in the art that Jiao of coke gasification gained in the present invention
The composition of charcoal gas is the simplest, thus the purified treatment of described coke gas is the easiest, no
Need individually to carry out tar separation and methane conversion processing.It addition, in the present invention, STRENGTH ON COKE system
When gas carries out desulfurization process, compared to coke-stove gas, in coke gas, organic sulfur accounts for total sulfur content
Ratio is lower, it is easier to removing, its sulfur method is known in the art, such as dry desulfurization and
Wet desulphurization, repeats no more here.
The method according to the invention, purifies first gas and second and purifies gas mixing, profit in step e
Ethylene glycol is prepared with the unstripped gas obtained.The present invention first purifies gas (i.e. coke oven after purified treatment
Coal gas) in, feature based on carbonization of coal self, its hydrogen content apparently higher than carbon monoxide,
Not less than 3.5 times of carbon monoxide, there is hydrogen when being used for preparing ethylene glycol superfluous in such as hydrogen content,
Therefore current coke-stove gas generally designs to the yield of ethylene glycol on the basis of carbon monoxide content.Separately
Outward, purify in gas (i.e. coke gas after desulfurization) second, spy based on coke gasification self
Point, its carbon monoxide content is not less than 1.2 times of hydrogen higher than hydrogen, such as carbon monoxide content,
Similar to coal direct gasification gained synthesis gas, when for preparing ethylene glycol, need also exist for the most logical
Cross conversion section regulation C/Hratio.The present invention purifies first gas and second and purifies gas mixing, gained
In unstripped gas, the thing mass ratio of carbon monoxide and hydrogen is close to the theory demands ratio of synthesizing glycol,
Compared with coal direct gasification gained synthesis gas, it is not necessary to regulated C/Hratio further by conversion section.
The method of basic invention, it is preferable that in the gas that step b obtains, the volume of carbon monoxide contains
Amount is 13%～19%, and the volume content of hydrogen is 68%～74%；Second purifies carbon monoxide in gas
Volume content be 42%～48%, the volume content of hydrogen is 32%～38%.It is further preferred that
In the gas that step b obtains, the volume content of carbon monoxide is 14%～18%, the volume content of hydrogen
It is 69%～73%；In second purification gas, the volume content of carbon monoxide is 43%～47%, hydrogen
Volume content is 33%～37%.It is further preferred that carbon monoxide in the gas that obtains of step b
Volume content be 15%～17%, the volume content of hydrogen is 70%～72%；Second purifies in gas
The volume content of carbon monoxide is 44%～46%, and the volume content of hydrogen is 34%～36%.
Method in accordance with the invention it is preferred that described step e particularly as follows:
F, from described unstripped gas, isolated carbon monoxide product gas and hydrogen by pressure swing adsorption method produce
Product gas；
G, by oxalic acid ester process synthesizing glycol；Utilize oxalic acid ester process synthesizing glycol for this area institute
Know, repeat no more here.
The method according to the invention, it is further preferred that in step f, for the raw material of the present invention
Gas, passes through CO2Carbon dioxide in pressure-swing absorber removing unstripped gas, obtains carbon dioxide removal
Unstripped gas；Wherein it is preferred to, described CO2Pressure-swing absorber is provided with Sichuan Dakot CC
DKT-200 type CO produced2Adsorbent；
By CO pressure-swing absorber, the carbon monoxide in the unstripped gas after carbon dioxide removal is extracted
Out, obtain carbon monoxide product gas, wherein it is preferred to, described CO pressure-swing absorber sets
There is the DKT-812 type CO adsorbent that Sichuan Dakot CC produces；
By hydrogen cleaning pressure-swing absorber to remaining gas in addition to the hydrogen in remaining unstripped gas
Carry out adsorbing and removing, to obtain hydrogen product gas, wherein it is preferred to, described hydrogen cleaning transformation
Being sequentially provided with the mass ratio produced by Sichuan Dakot CC in adsorption tower along airflow direction is 0.9～1.1:
DKT-15B, DKT-300a and DKT-300b type adsorbent of 0.9～1.1:0.9～1.1, further
Preferably, described mass ratio is 1:1:1.From described unstripped gas, an oxidation is isolated by the method
When carbon products gas and hydrogen product gas, the yield of carbon monoxide is not less than 85%, and purity is not less than 99
Mol%；Hydrogen yield is not less than 89%, and purity is not less than 99mol%, good separating effect.
Compared with prior art, the invention have the advantages that
1, the method for the present invention proposes a kind of new coal-ethylene glycol and coke utilizes thinking, right
In China, coking industry is significant, owing to China's steel industry presently, there are serious production capacity surplus,
So that Coke Industry exists problem of excess production capacity accordingly, the coke that the present invention is given utilizes to be thought
Road so that coke production enterprise is in the case of steel industry is stagnant, and its production capacity can be unlikely to
Idle, waste, has broken away from impact and the constraint of steel industry STRENGTH ON COKE industry, reverses coking industry
The situation generally lost at present, drives the development of Coke Industry.
2, in the present invention, higher according to hydrogen gas in coke oven gas content, and an oxygen in coke gas
Change the higher feature of carbon content, both mixed so that unstripped gas when being used for preparing ethylene glycol without
Need the making full use of of effective ingredient in transformed workshop section regulation C/Hratio, beneficially gas, improve warp
Ji benefit.
Detailed description of the invention
Below in conjunction with specific embodiment, the present invention will be described, but the present invention is not limited to this.
Embodiment 1
Flow from coking furnace is about 30000Nm3The coke-stove gas of/h sequentially passes through tar and divides
After, desulfurization and methane conversion processing, the coke-stove gas after being purified, its flow is about 47000
Nm3/ h, the main component of the coke-stove gas after described purification is shown in Table 1:
Table 1
| Component | N2(mol%) | CH4(mol%) | CO (mol%) | CO2(mol%) | Ar (mol%) | H2(mol%) |
| Coke-stove gas | 1.31 | 1.06 | 16.01 | 9.24 | 0.43 | 71.95 |
| Coke gas | 1.10 | 0.40 | 45.80 | 17.50 | 0.20 | 35.00 |
Embodiment 2
Coke from coking furnace is sent into fixed-bed gasification furnace and carries out gasification process, gasification process bar
Part is: with 6-50mm coke button as raw material, with steam and oxygen as gasifying agent, at average pressure
Under conditions of about 0.1MPa, mean temperature about 1280 DEG C, carry out gasification reaction and generate coke gas,
Wherein, the consumption of described steam is 1.8 ton/ton coke, and the consumption of described oxygen is 470Nm3/
Ton coke, the consumption of described coke is about 17 ton hour, accounts for the coke total output of coking furnace
1/3.Described coke gas is after dedusting, desulfurization process, and the flow of the coke gas obtained is about
38000Nm3/ h, main component is shown in Table 1.
Embodiment 3
Jiao after the desulfurization that coke-stove gas after the purification obtain embodiment 1 and embodiment 2 obtain
Charcoal gas mixes, and in unstripped gas, carbon monoxide is about 1:2 with the volume ratio of hydrogen.By gained unstripped gas
Pass through CO2Carbon dioxide in pressure-swing absorber removing unstripped gas, obtains the former of carbon dioxide removal
Material gas；Wherein, described CO2Pressure-swing absorber is provided with the DKT-200 that Sichuan Dakot CC produces
Type CO2Adsorbent；By CO pressure-swing absorber by the unstripped gas after carbon dioxide removal
Carbonoxide extracts, and obtains carbon monoxide product gas, wherein, in described CO pressure-swing absorber
It is provided with the DKT-812 type CO adsorbent choosing that Sichuan Dakot CC produces；Become by hydrogen cleaning
Pressure adsorption tower carries out adsorbing and removing to remaining gas in addition to the hydrogen in remaining unstripped gas, with
To hydrogen product gas, wherein, described hydrogen cleaning pressure-swing absorber is sequentially provided with along airflow direction
The mass ratio produced by Sichuan Dakot CC be 1:1:1 DKT-15B, DKT-300a and
DKT-300b type adsorbent.Isolated carbon monoxide product throughput is 21298Nm3/ h is pure
Degree is not less than 99mol%；Isolated hydrogen product throughput is 42233.16Nm3/ h, purity is not
Less than 99.9mol%.
Embodiment 4
The carbon monoxide product gas and the hydrogen product gas that embodiment 3 are prepared pass through oxalate further
Method synthesizing glycol, ethylene glycol yield is about 25 ton hour, and ethylene glycol yield is about 85%.
Secondary metallurgical price is about 759 yuan/ton at present, and suitable with production cost, enterprise is difficult to be full of
Profit.
After using the present invention, the coking production capacity of coke-oven plant about 1/3 can be consumed, it is ensured that coking
The oepration at full load of factory, by coke gasification, further synthesizing glycol, per hour coke consumption 17
Ton, generation ethylene glycol 25 tons, the selling price of ethylene glycol is about 6000 yuan/ton, the production time in year
Calculated by 300 days, compared with selling coke, every annual sales amount increase about 9.8 hundred million yuan, directly, indirectly
Profit is the most considerable, and also can keep relevant auxiliary facility (such as, supporting coal washery and
Tar purification workshop section) normal operation.
Claims (10)
1. utilize coke-stove gas to supplement the method that coke gas gained unstripped gas prepares ethylene glycol,
Described method includes:
A, utilize coal coking, obtain coke and coke-stove gas；
B, the coke-stove gas obtaining step a carry out purified treatment, obtain the first purification gas；
C, the coke obtaining step a gasify, and obtain coke gas；
D, the coke gas obtaining step c carry out purified treatment, obtain the second purification gas；
E, by described first purify gas and second purify gas mixing, and utilize mixing gained unstripped gas system
Standby ethylene glycol.
Method the most according to claim 1, it is characterised in that in step c, STRENGTH ON COKE
When gasifying, with steam and oxygen as gasifying agent, fixed bed STRENGTH ON COKE is utilized to gasify,
Vapor pressure be 0.09～0.11MPa pressure, gasification temperature be 1100～1300 DEG C, gasification coke
It is 6～50mm coke buttons.
Method the most according to claim 2, it is characterised in that the consumption of described steam is
1.7～2.0 ton/ton coke, the consumption of described oxygen is 460～500Nm3/ ton coke.
Method the most according to claim 3, it is characterised in that described vapor pressure is normal pressure,
Gasification temperature is 1150～1250 DEG C.
Method the most according to claim 4, it is characterised in that the consumption of described steam is
1.8～1.9 ton/ton coke, the consumption of described oxygen is 475～485N m3/ ton coke.
6. according to the method according to any one of claim 1-5, it is characterised in that step b obtains
To gas in the volume content of carbon monoxide be 13%～19%, the volume content of hydrogen is
68%～74%；In second purification gas, the volume content of carbon monoxide is 42%～48%, the volume of hydrogen
Content is 32%～38%.
Method the most according to claim 6, it is characterised in that in step c, for Jiao
The amount of coke of charcoal gas is 0.3～0.4 times of coke output in step a.
Method the most according to claim 1, it is characterised in that described step e particularly as follows:
F, from described unstripped gas, isolated carbon monoxide product gas and hydrogen by pressure swing adsorption method produce
Product gas；
G, by oxalic acid ester process synthesizing glycol.
Method the most according to claim 8, it is characterised in that in step f, passes through CO2
Carbon dioxide in pressure-swing absorber removing unstripped gas, obtains the unstripped gas of carbon dioxide removal；
By CO pressure-swing absorber, the carbon monoxide in the unstripped gas after carbon dioxide removal is extracted
Out, carbon monoxide product gas is obtained；
By hydrogen cleaning pressure-swing absorber to remaining gas in addition to the hydrogen in remaining unstripped gas
Carry out adsorbing and removing, to obtain hydrogen product gas.
Method the most according to claim 9, it is characterised in that described CO2Pressure-variable adsorption
Tower is provided with DKT-200 type CO that Sichuan Dakot CC produces2Adsorbent；
Described CO pressure-swing absorber is provided with DKT-812 type CO that Sichuan Dakot CC produces
Adsorbent；
Described hydrogen cleaning pressure-swing absorber is sequentially provided with Sichuan Dakot CC along airflow direction raw
Produce DKT-15B, DKT-300a that mass ratio is 0.9～1.1:0.9～1.1:0.9～1.1 and
DKT-300b type adsorbent.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510052532.4A CN105985221A (en) | 2015-02-02 | 2015-02-02 | Method for preparing ethylene glycol by using raw material gas obtained through supplementing coke-oven gas to coke gasified gas |
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| CN201510052532.4A CN105985221A (en) | 2015-02-02 | 2015-02-02 | Method for preparing ethylene glycol by using raw material gas obtained through supplementing coke-oven gas to coke gasified gas |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107973270A (en) * | 2017-10-12 | 2018-05-01 | 东华工程科技股份有限公司 | A kind of coke-stove gas mends carbon conversion preparing ethylene glycol synthesis gas process |
| CN109111341A (en) * | 2018-07-25 | 2019-01-01 | 戴乐亭 | The method of coke-stove gas and converter and/or blast furnace gas synthesizing glycol coproduction LNG |
-
2015
- 2015-02-02 CN CN201510052532.4A patent/CN105985221A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107973270A (en) * | 2017-10-12 | 2018-05-01 | 东华工程科技股份有限公司 | A kind of coke-stove gas mends carbon conversion preparing ethylene glycol synthesis gas process |
| CN109111341A (en) * | 2018-07-25 | 2019-01-01 | 戴乐亭 | The method of coke-stove gas and converter and/or blast furnace gas synthesizing glycol coproduction LNG |
| CN109111341B (en) * | 2018-07-25 | 2021-10-08 | 戴乐亭 | Method for synthesizing ethylene glycol and co-producing LNG (liquefied natural gas) by using coke oven gas and converter and/or blast furnace gas |
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Application publication date: 20161005 |