CN103214334A - Thermoelectricity combined production method and apparatus for preparing alkene and by coal and natural gas - Google Patents
Thermoelectricity combined production method and apparatus for preparing alkene and by coal and natural gas Download PDFInfo
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Abstract
The invention relates to a thermoelectricity combined production method and apparatus for preparing alkene and by coal and natural gas, and the method comprises the following steps: (1) separating coal, steam and air for obtaining oxygen, gasifying oxygen for obtaining water gas by reaction, and purifying for obtaining coal-based synthetic gas; carrying out a reforming reaction from natural gas and carbon dioxide and obtaining a natural gas-based synthetic gas; (2) synthesizing methanol using the coal-based synthetic gas in the step (1) or using the coal-based synthetic gas and the natural gas-based synthetic gas; (3) separating the unreacted gas in the step (2) into three parts, and the first part is used for synthesizing methanol in the step (2), and the second part is used as fuel for providing heat for the natural gas reforming reaction, and the third part is used for power generation and heat supply for the gas turbine; (4) separating the methanol in the step (2) into two parts, and one part is used for preparing alkene and generating water; and the other part is used for the reforming reaction with the generated water for preparing hydrogen and carbon dioxide, and separating hydrogen and carbon dioxide, and synthesizing ammonia from the obtained hydrogen and nitrogen separated from air, wherein, the obtained carbon dioxide by separation is used for the natural gas reforming reaction.
Description
Technical field
The invention relates to a kind of coal and Sweet natural gas and produce the cogeneration method and the device of alkene and ammonia.
Background technology
Ethene, propylene are the most basic raw materials of petrochemical industry, and the output of ethene just is considered to the sign of national economic development level, and along with the development of China's economy and society, still can keep the higher rigidity demand future.Traditional ethylene production is a raw material with ethane, propane, petroleum naphtha, LIGHT DIESEL OIL mainly, by the tube furnace preparing ethylene by steam cracking, but Chinese lighter hydrocarbons and petroleum resources are very limited, can not satisfy ethene lighting ingredient requirement, and rising steadily of crude oil price and increasing the weight of of crude oil poor qualityization phenomenon, make that the product cost of traditional ethylene production is higher.In recent years, several novel ethene preparation methods that grow up both at home and abroad.
More advanced method has Sweet natural gas system ethene, low-carbon alkene system ethene, coal-methanol-to-olefins etc. several at present.In the Sweet natural gas system ethene method, at first need to carry out producing synthetic gas by natural gas conversion, be used for synthesizing alkene then, the major advantage of this method is that flow process is short, lower, the CO of facility investment
2Discharging is few.But the synthetic gas that gas renormalizing makes often hydrogen-carbon ratio is higher, and the synthetic gas hydrogen-carbon ratio that adopts typical natural gas steam reforming to obtain is generally 2.5～3.0, often needs to replenish CO before derived product is synthetic
2Reduce H
2/ CO needs the additive decrementation energy, and needs a large amount of heats during conversion of natural gas, and the fuel natural gas that needs accounts for 1/3 of Sweet natural gas total burn-off, and gas consumption is big.If can replace the bigger fuel natural gas of consumption in traditional method for transformation with other cheap fuel, will significantly reduce production costs.
With the coal is that raw material is produced in the method for ethene, because hydrogen-carbon ratio is on the low side in the synthetic gas that makes, is generally less than 1, and derived product often needs to carry out gas conversion when synthetic, with CO and H
2The O reaction generates H
2And CO
2Improve H
2/ CO has increased CO in the conversion process
2To the discharging of environment, and reclaiming CO
2, remove CO
2With need to consume additional energy in the process of CO conversion, make that the energy utilization efficiency of system is lower.
Summary of the invention
The cogeneration method that provides a kind of coal and Sweet natural gas to produce alkene and ammonia is provided one object of the present invention.
Another object of the present invention is to provide a kind of device that is used to realize aforesaid method.
For reaching above-mentioned purpose, on the one hand, the invention provides the cogeneration method that a kind of coal and Sweet natural gas are produced alkene and ammonia, described method comprises the steps:
(1) preparation of synthetic gas: the oxygen that coal and water vapour, air separation are obtained carries out gasification reaction and obtains water-gas, and water-gas obtains producing synthesis gas from coal through purifying; Sweet natural gas and carbonic acid gas or water vapour are carried out reforming reaction, obtain the Sweet natural gas preparing synthetic gas;
(2) preparation of methyl alcohol: the producing synthesis gas from coal that step (1) is obtained or itself and Sweet natural gas preparing synthetic gas be mixed for synthesizing methanol;
(3) utilization of unreacting gas: unreacted gas in step (2) the synthesizing methanol process is divided into three parts, first part of circulation is used for the synthesizing methanol of step (2), second part acts as a fuel and provides heat to gas renormalizing reaction, and the 3rd part is used for gas turbine power generation and heat supply;
(4) preparation of the preparation of alkene and ammonia: the methyl alcohol that step (2) is obtained is divided into two parts, and portion is used for preparing alkene and this process produces water; The water that produces in another part methyl alcohol and the preparation olefin hydrocarbon carries out reforming reaction, preparation hydrogen and carbonic acid gas, separating hydrogen gas and carbonic acid gas, the nitrogen that hydrogen that separation is obtained and air separation obtain is mixed for synthetic ammonia, separates the carbonic acid gas that obtains and is used for the gas renormalizing reaction.
According to method of the present invention, in the step (1), the usage ratio of coal, water vapour and oxygen can be carried out according to the prior art ratio, the preferred described coal gasification reaction condition of the present invention is: pressure 0～10MPa, 1000～1600 ℃ of temperature, and the usage ratio of control coal, water vapour and oxygen makes, and hydrogen-carbon ratio is 0.4～0.7 in the described producing synthesis gas from coal that obtains;
According to method of the present invention, in the step (1), the usage ratio of Sweet natural gas and carbonic acid gas can be carried out according to the prior art ratio, the preferred described gas renormalizing reaction conditions of the present invention is 700～950 ℃ of pressure 1.0～2.5MPa, temperature, and the consumption of control Sweet natural gas and carbonic acid gas make hydrogen-carbon ratio in the described Sweet natural gas preparing synthetic gas that obtains be 1 or the consumption of controlling Sweet natural gas and water vapour make that hydrogen-carbon ratio is 3 in the described Sweet natural gas preparing synthetic gas that obtains.
The present invention is further preferred, and the input quality of control raw natural gas and coal is 0～2.3, is preferably 2.3.
When the input quality ratio of raw natural gas and coal was 2.3, the mixed hydrogen-carbon ratio of Sweet natural gas preparing synthetic gas and producing synthesis gas from coal met the best requirement of methyl alcohol synthetic.Hydrogen-carbon ratio of the present invention is a mol ratio.
Wherein, the synthetic gas that preferred reforming reaction produces reclaims heat in interchanger, be used for preheating Sweet natural gas and mixture of steam, is used to produce saturation steam subsequently.
According to method of the present invention, in the step (1), preferred described aftertreatment can be with reference to the similar post processing mode of prior art, the present invention is not to be improvement to post processing mode, yet in order further to improve effect of the present invention, the preferred aftertreatment of the present invention is for to reclaim the high temperature sensible heat with water-gas, and except that deashing, carry out desulfurization then and handle, further reclaim heat after the desulfurization;
Described desulfurization is handled can be the sulfur method of prior art, and the further preferred described desulfurization of the present invention is treated to wet desulphurization, more preferably low-temperature rectisol method or polyglycol dimethyl ether process.
According to method of the present invention, after preferably handling through described desulfurization, water-gas total sulfur content≤10mg/Nm
3
The described pre-treatment of step of the present invention (1) can be any pretreatment process of state of the art, and the preprocessing process that the present invention preferably adopts comprises coal separation, drying, fragmentation, screening.Coal can be sneaked into many impurity in the process of exploitation and be caused pit ash to increase, and the purpose of coal separation is exactly in order to remove major impurity in the coal, to reduce ash content and sulphur content.Adopt drying means to reduce moisture in coal then, thereby improve the thermal value of coal, be beneficial to transportation simultaneously, drying plant generally adopts revolving drier.Broken coal mainly adopts ring hammer crusher, and the feed coal of this kind equipment fragmentation can guarantee granularity less than 10mm, after screening, the coal of release mesh is sent into vapourizing furnace again.
Generally, to need behind gas conversion recirculation to be used for methyl alcohol synthetic for first part of step (3) unreacted gas.When the mass ratio of Sweet natural gas and coal is 2.3, can remove described gas conversion reaction from.
According to method of the present invention, the described synthesizing methanol reaction conditions of preferred steps (2) is 200～300 ℃ of pressure 4～10MPa, temperature.
The present invention preferably mixes producing synthesis gas from coal and Sweet natural gas preparing synthetic gas also that the back is compressed earlier, be sent to the methyl alcohol synthetic reactor synthesizing methanol after the preheating.
According to method of the present invention, first part of unreacted gas of preferred steps (3) carries out gas conversion through at pressure 5MPa under the condition that temperature is 250 ℃, and circulating then, it is synthetic to be used for methyl alcohol.
According to method of the present invention, the 3rd part of unreacting gas of preferred steps (3) is used for generating and heat supply is, unreacting gas is sent to the gas turbine combustion acting, and the high-temperature flue gas of discharge and boiler hot exchange produce hot steam, are used to drive steam turbine and heat supply.
According to method of the present invention, the condition of this preparation alkene of preferred steps (4) is 400～550 ℃ of pressure 0.2～0.5MPa, temperature, and sieves as catalyzer with the silicon aluminium phosphate molecules of salt.
According to method of the present invention, the described reforming reaction condition of preferred steps (4) is that temperature is 250～300 ℃, and pressure is 1～5MPa.
According to method of the present invention, step (4) synthetic ammonia can synthesize according to art methods, and the reaction conditions that the present invention preferably adopts is: pressure is 20～50MPa, and temperature is 400～500 ℃.
According to method of the present invention, the nitrogen of step (4) synthetic ammonia comes from prior art, such as the nitrogen that can adopt air separation equipment to provide, perhaps commercial any nitrogen.
According to method of the present invention, producing synthesis gas from coal that preferred steps (1) obtains and Sweet natural gas preparing synthetic gas temperature are 40 ℃.
Wherein the present invention can more specifically be:
A kind of coal and Sweet natural gas are produced the cogeneration method of alkene and ammonia, and this method specific implementation method may further comprise the steps:
Feed coal carries out gasification reaction with water vapour, oxygen under the condition of 1000～1600 ℃ of pressure 0～10MPa and temperature after pre-treatment, mainly contained CO, H
2, CO
2Water-gas, water-gas reclaims the high temperature sensible heat through waste heat boiler, is sent to tripping device and removes and deash.
Adopt low-temperature rectisol method or domestic more sophisticated polyglycol dimethyl ether process (NHD method) or other wet desulphurization technology, water-gas is purified to total sulfur content≤10mg/Nm after desulfurization is handled
3, further reclaim heat and be cooled to obtain producing synthesis gas from coal about 40 ℃.
Sweet natural gas carries out reforming reaction with carbonic acid gas under the condition of 700～950 ℃ of pressure 1.0～2.5MPa, temperature, the synthetic gas that produces reclaims heat in interchanger, be used for preheating Sweet natural gas and mixture of steam, be used to produce saturation steam subsequently, synthetic gas is cooled to obtain the Sweet natural gas preparing synthetic gas about 40 ℃.
Described producing synthesis gas from coal and Sweet natural gas preparing synthetic gas are directly mixed, be sent to methyl alcohol synthetic reactor after compressed, the preheating, in pressure 4～10MPa, 200～300 ℃ of reactions down of temperature, the reaction product that synthetic tower is discharged is after cooling, isolate thick methyl alcohol, thick methyl alcohol obtains refined methanol through rectifying.
The unreacting gas of methyl alcohol building-up process is divided into three parts, and a circulation synthesizing methanol that continues carries out the hydrogen-carbon ratio that gas conversion is adjusted methyl methanol syngas to carrying out this part of round-robin unreacting gas.
Second part of unreacting gas in the methyl alcohol building-up process is used for replacing Sweet natural gas, is sent in the gas renormalizing reactor combustion chamber as fuel and burns, provide the gas renormalizing process needed heat.
The 3rd part of unreacting gas in the methyl alcohol building-up process is sent to the gas-turbine combustion chamber burning, the combustion gas that produces High Temperature High Pressure is discharged from the combustion chamber, send into the turbine expansion acting then, the high-temperature flue gas of discharge reclaims sensible heat through waste heat boiler and produces superheated vapour, drives steam turbine generating and heat supply.
The methyl alcohol that makes under the condition of 400～550 ℃ of pressure 0.2～0.5MPa, temperature, is sent into methanol to olefins reaction device (MTO reactor), contact with silicon aluminium phosphate molecules of salt sieve catalyst.Make methanol conversion become to contain the product stream of ethene, propylene.
With the water that produces in the methanol-to-olefins process and intermediate product methyl alcohol at 250～300 ℃, reforming reaction takes place under the condition of 1～5MPa, produce hydrogen and carbonic acid gas, reformate comes hydrogen and carbon dioxide separation through transformation absorption, and the nitrogen that separation is obtained hydrogen and air separation process generation carries out ammonia synthesis reaction and produces ammonia.
On the other hand, the present invention also provides a kind of device that is used to realize the method for the invention, and this device comprises:
Air separation plant, being used for air separation is oxygen and nitrogen;
Vapourizing furnace, the oxygen that is used to provide coal and water vapour, air separation to obtain carries out gasification reaction and obtains water-gas;
Refining plant, the coal gas that is used to purify waste water obtains producing synthesis gas from coal;
Reforming reactor is used to provide Sweet natural gas and carbonic acid gas to carry out reforming reaction and obtains the Sweet natural gas preparing synthetic gas;
Methanol synthesizer is used for producing synthesis gas from coal and Sweet natural gas preparing synthetic gas mixing synthesizing methanol; And this methanol synthesizer is provided with and is used for part unreacting gas in it is drawn methanol synthesizer is recycled into methanol synthesizer behind gas conversion pipeline; Also be provided with the part unreacting gas is drawn the pipeline that methanol synthesizer is sent to the reforming reaction device; Also be provided with the part unreacting gas is drawn the pipeline that methanol synthesizer is sent to power generation assembly;
Power generation assembly is used to accept the part unreacting gas from methanol synthesizer, by gas turbine power generation and heat supply;
The alkene synthesizer, being used for the methyl alcohol from methanol synthesizer is the synthetic alkene of raw material, and produces water;
The methanol recapitalization device, be used for being that raw material carries out reforming reaction and prepares hydrogen and carbonic acid gas from the methyl alcohol of methanol synthesizer and from the water of alkene synthesizer, and this device is provided with the equipment of separating hydrogen gas and carbonic acid gas, and is provided with the pipeline that carbonic acid gas is delivered to the gas renormalizing reactor;
Ammonia synthesizer is used to accept finish the ammonia synthesis reaction of hydrogen and nitrogen from the hydrogen of methanol recapitalization device and from the nitrogen of air separation plant.
In sum, the invention provides cogeneration method and the device that a kind of coal and Sweet natural gas are produced alkene and ammonia.The method of the invention has following advantage: the technology of the present invention combines two kinds of raw materials produces olefin product, remedied the serious unbalanced problem of simple employing coal or gas material hydrogen-carbon ratio, change than in 0～2.3 scope by the input quality that changes raw natural gas and coal, the hydrogen-carbon ratio of methyl methanol syngas is changed between 0～2, thereby reduce the degree of depth of synthetic gas conversion, make the energy consumption and the CO of this process
2Discharge lowly, when two kinds of raw materials quality ratios are 2.3, can remove the gas conversion unit from.This technology adopts part unreacting gas alternative fuel Sweet natural gas simultaneously, as the fuel of gas renormalizing reactor, provides the heat of gas renormalizing needs, can reduce the consumption of Sweet natural gas, significantly reduces the production cost of alkene.
This technology is reformed the water and the intermediate product methyl alcohol that produce in the methanol-to-olefins process, can reduce the energy wastage and the sewage discharge of this process, the hydrogen that generates can be used for synthetic ammonia with nitrogen, the utilization of this reasonable in technology the synthetic gas of different compositions and the intermediate product in the process, realized the comprehensive utilization of the energy, reduce product energy consumption, reached the purpose of recycling economy.
Description of drawings
Fig. 1 is the process flow sheet of the embodiment of the invention 1;
Fig. 2 is the process flow sheet of the embodiment of the invention 2;
Fig. 3 is the process flow sheet of the embodiment of the invention 3.
Embodiment
Below describe the beneficial effect of implementation process of the present invention and generation in detail by specific embodiment, be intended to help the reader to understand essence of the present invention and characteristics better, but not as qualification to this case practical range.
Embodiment 1
Fig. 1 produces the process flow sheet of the cogeneration process implementing example one of alkene and ammonia for coal of the present invention and Sweet natural gas.This embodiment is a raw material with coal and Sweet natural gas, adopts existing mature technology to prepare synthetic gas.Wherein be raw material when producing synthetic gas with the coal, can adopt U.S. Texaco air flow bed coal water slurry gasification technology, Dutch Shell fine coal gas pressurized gasification technology, the hydrogen-carbon ratio in the producing synthesis gas from coal is 0.4～0.7; Be that raw material adopts the methane carbon dioxide reformation technology when producing synthetic gas with the Sweet natural gas.The synthetic gas hydrogen-carbon ratio that the methane carbon dioxide reformation technology makes is 1, and synthetic gas need be adjusted hydrogen-carbon ratio through gas conversion and make it to reach the best hydrogen-carbon ratio of methyl alcohol synthetic 2: 1 usually.After in this example two portions synthetic gas being mixed, without gas conversion, it is synthetic directly to send to methyl alcohol, carries out the gas reforming rate that gas conversion improves the methyl alcohol building-up process and needs are carried out that part of unreacted synthesis gas of round-robin.The oxygen that needs in the synthetic gas production process by coal gasification is provided by air separation facility, the carbonic acid gas that carbonic acid gas that the carbonic acid gas that needs in the Sweet natural gas synthetic gas production process can remove from the gas conversion device or intermediate product methanol recapitalization generate.Describe the cogeneration technology that coal in the embodiment of the invention and Sweet natural gas are produced alkene and ammonia below in detail.
Feed coal and water vapour, oxygen carry out gasification reaction under the condition of 1200 ℃ of pressure 5.2MPa and temperature, obtain raw gas, raw gas is sent to tripping device except that deashing after waste heat boiler reclaims the high temperature sensible heat, be cooled to about 40 ℃ through purifying and further reclaiming heat, obtain producing synthesis gas from coal, hydrogen-carbon ratio is 0.4.
Sweet natural gas and carbonic acid gas carry out conversion reaction under the condition of 860 ℃ of pressure 2.5MPa, temperature, the synthetic gas of generation reclaims heat and produces saturation steam, continues to be cooled to 40 ℃, obtains the Sweet natural gas preparing synthetic gas, and hydrogen-carbon ratio is 1 in the synthetic gas.
The producing synthesis gas from coal and the Sweet natural gas preparing synthetic gas that obtain are directly sent to methanol synthesizer after the mixing, the input quality ratio of control raw natural gas and coal is 2.3 o'clock, and producing synthesis gas from coal that obtains and Sweet natural gas preparing synthetic gas mix the back hydrogen-carbon ratio and meet the best requirement of methyl alcohol synthetic.In pressure 5MPa, 250 ℃ of reactions down of temperature, the reaction product that synthetic tower is discharged is isolated thick methyl alcohol after cooling, and thick methyl alcohol obtains refined methanol through rectifying.
Unreacting gas in the methyl alcohol building-up process can be divided into three parts flexibly according to the price and the demand of product methyl alcohol and power product, portion issues angry body conversion in pressure 5MPa, 225 ℃ of conditions of temperature, methanol synthesizer is sent in gas removal carbonic acid gas circulation after the conversion, and its ratio that accounts for unreacting gas is 0.2～0.8 (is 1 with unreacting gas).
Second part of unreacting gas is used for replacing Sweet natural gas, acts as a fuel to be sent in the gas renormalizing reactor combustion chamber and burn, provide the gas renormalizing process needed heat, its ratio that accounts for unreacting gas is 0.2～0.3;
The 3rd part of unreacting gas in the methyl alcohol building-up process is sent to the gas-turbine combustion chamber burning, the combustion gas that produces 1260 ℃ High Temperature High Pressure is discharged from the combustion chamber, send into the turbine expansion acting then, 560 ℃ the high-temperature flue gas of discharging reclaims sensible heat through waste heat boiler and produces superheated vapour, the generating of driving steam turbine, its portion is 0.2～0.8.
The methyl alcohol produced under pressure 0.4MPa, 450 ℃ of conditions of temperature, is sent into the MTO reactor, methanol feedstock is contacted with silicon aluminium phosphate molecules of salt sieve catalyst.Make methanol conversion become the low-carbon alkene product.
Reforming reaction takes place in the methyl alcohol that the water that produces in the methanol-to-olefins process and step (2) are obtained under 250 ℃, the condition of 5MPa, produce hydrogen and carbonic acid gas, reformate comes hydrogen and carbon dioxide separation through transformation absorption, and the nitrogen that separation is obtained hydrogen and air separation process generation carries out ammonia synthesis reaction and produces ammonia under the condition of 500 ℃ of pressure 20MPa, temperature.
The isolating oxygen of air separation process is used for producing producing synthesis gas from coal as the oxygenant of coal gasification course, and the carbonic acid gas that the methanol recapitalization reaction obtains can be used as the raw material of gas renormalizing process and produces synthetic gas.
Embodiment 2
Fig. 2 produces the process flow sheet of the cogeneration process implementing example two of alkene and ammonia for coal of the present invention and Sweet natural gas, be that raw material is produced synthetic gas with the coal among this embodiment, can adopt U.S. Texaco air flow bed coal water slurry gasification technology, Dutch Shell fine coal gas pressurized gasification technology; Be that raw material adopts gas water steam reforming technology when producing synthetic gas with the Sweet natural gas.Hydrogen-carbon ratio is higher in the synthetic gas that gas water steam reforming technology makes, be generally 2.5～3.0, can be by adjusting the mass ratio of feed coal and Sweet natural gas, producing synthesis gas from coal and Sweet natural gas preparing synthetic gas are combined according to the ratio that presets, make it to meet the best hydrogen-carbon ratio of methyl alcohol synthetic, mixed synthesis gas is directly sent to synthesizing methanol, the unreacting gas of methyl alcohol building-up process partly circulates and improves the transformation efficiency of synthetic gas, the water that needs in the Sweet natural gas synthetic gas production process is from the process water that produces in the production process, and the oxygen that needs in the synthetic gas production process by coal gasification is provided by air separation facility.Describe the cogeneration technology that coal in the embodiment of the invention and Sweet natural gas are produced alkene and ammonia below in detail.
Feed coal and water vapour, oxygen carry out gasification reaction and produce producing synthesis gas from coal under the condition of 1200 ℃ of pressure 5.2MPa and temperature, hydrogen-carbon ratio is 0.4 in the synthetic gas.
Sweet natural gas and water vapour are produced the Sweet natural gas preparing synthetic gas under the condition of 860 ℃ of pressure 2.5MPa, temperature, hydrogen-carbon ratio is 3 in the synthetic gas.
The producing synthesis gas from coal and the Sweet natural gas preparing synthetic gas that obtain are directly sent to methanol synthesizer after the mixing, the input quality ratio of control raw natural gas and coal is 2.3 o'clock, make the hydrogen-carbon ratio in the synthetic gas meet the requirement of methyl alcohol synthetic optimum proportion, send to methanol synthesizer then, produce thick methyl alcohol in pressure 5MPa, 250 ℃ of following reactions of temperature, thick methyl alcohol obtains refined methanol through rectifying.
Unreacting gas in the methyl alcohol building-up process is divided into three parts flexibly according to the price and the demand of product methyl alcohol and power product, first part of unreacting gas carries out gas circulation to be sent to methanol synthesizer to proceed methyl alcohol synthetic, and its ratio that accounts for unreacting gas is 0.2～0.8; Second part of unreacting gas is used for replacing Sweet natural gas, acts as a fuel to be sent in the gas renormalizing reactor combustion chamber to burn, and provides the gas renormalizing process needed heat, and its ratio that accounts for unreacting gas is 0.2～0.3;
The 3rd part of unreacting gas in the methyl alcohol building-up process is sent to the gas-turbine combustion chamber burning, the combustion gas that produces 1260 ℃ High Temperature High Pressure is discharged from the combustion chamber, send into the turbine expansion acting then, 560 ℃ the high-temperature flue gas of discharging reclaims sensible heat through waste heat boiler and produces superheated vapour, the generating of driving steam turbine, its portion is 0.2～0.8.
The methyl alcohol that makes under pressure 0.4MPa, 450 ℃ of conditions of temperature, is sent into the MTO reactor and produced the low-carbon alkene product.Simultaneously the water that produces in the methanol-to-olefins process and intermediate product methyl alcohol under 250 ℃, the condition of 5MPa reforming reaction are taken place, produce hydrogen and carbonic acid gas, reformate comes hydrogen and carbon dioxide separation through transformation absorption.
Separation is obtained nitrogen that hydrogen and air separation process produce to be carried out ammonia synthesis reaction and produces ammonia under the condition of 500 ℃ of pressure 20MPa, temperature.The isolating oxygen of air separation process is used for producing producing synthesis gas from coal as the oxygenant of coal gasification course.
Embodiment 3
In order to make technical scheme of the present invention and advantage clearer, analyze below in conjunction with 3 pairs of technologies of the present invention of specific embodiment, the above-mentioned Fig. 2 part of described process using the present invention flow process, this embodiment is a part of the present invention.This embodiment is to be the cogeneration technology that raw material is produced alkene with coal and Sweet natural gas, does not comprise ammonia synthesis technology.Key step is: carry out primary purifying and desulfurization after the gasification and handle, after the natural gas via reforming reaction with to carry out methyl alcohol after producing synthesis gas from coal mixes by a certain percentage synthetic and alkene is synthetic, methyl alcohol synthetic unreacting gas is divided into three parts, the portion synthesizing methanol that circulates, a as the unitary fuel of gas renormalizing, another part is sent to gas turbine power generation.Its schematic process flow diagram as shown in Figure 3.Feed coal is Tongchuan, Shaanxi coal, and the basal component of coal sees Table 1, and raw natural gas is from the area, Luzhou, and composition sees Table 2.
Table 1 Tongchuan coal compositional analysis and Lower heat value
Table 2 gas component
In this example, gasification adopts Texaco's air flow bed coal water slurry gasification technology, gas renormalizing adopts the steam reforming method, the synthetic strange low pressure synthetic technology in Shandong that adopts of methyl alcohol, the synthetic Dalian DMTO of the Chemistry and Physics Institute technology that adopts of alkene, synthesis gas components that comes out from coal gasifier and reforming reactor and state parameter are shown in table 3 and table 4.
Table 3 coal gasifier outlet synthesis gas components and state parameter
Table 4 reforming reactor outlet synthesis gas components and state parameter
This example utilization Aspen Plus software calculates Fig. 3 technology and coal system alkene technology.From economy, energy utilization situation, the tripartite analog result in the face of two kinds of technologies of environmental influence is analyzed comparison, gross investment, the cost of production unit alkene, system synthesis capacity usage ratio, unit consumption of energy, the C0 of main taking into account system
2These five indexs of quantity discharged.The cost of main raw material is:
Table 5 main raw material price
This project adopts economy, the energy of two kinds of technologies to utilize situation and emission reduction effect as shown in the table:
Two kinds of technologies of table 6 relatively
Wherein Firing Shenhua Coal system olefin process data are reported from the 3rd China energy scientist forum meeting.
As can be known from the above table, adopt the economy of explained hereafter alkene of the present invention to be higher than coal system olefin process, investment and alkene cost all have to a certain degree reduction.The present invention is a raw material with coal and Sweet natural gas, produces methyl alcohol, alkene, power product simultaneously, system, coupled degree height, and the energy situation of each link is good, compares with coal system olefin process, and the unit alkene energy consumption of this technology is lower, and the capacity usage ratio of system is higher.Because the present invention satisfies the synthetic requirement of methyl alcohol by regulating coal and Sweet natural gas ratio, does not need to carry out conversion, CO
2Quantity discharged reduces greatly.In sum, process synthesis of the present invention is functional, compares coal system alkene system and has clear superiority.
Claims (10)
1. coal and Sweet natural gas are produced the cogeneration method of alkene and ammonia, it is characterized in that described method comprises the steps:
(1) preparation of synthetic gas: the oxygen that coal and water vapour, air separation are obtained carries out gasification reaction and obtains water-gas, and water-gas obtains producing synthesis gas from coal through purifying; Sweet natural gas and carbonic acid gas or water vapour are carried out reforming reaction, obtain the Sweet natural gas preparing synthetic gas;
(2) preparation of methyl alcohol: the producing synthesis gas from coal that step (1) is obtained or itself and Sweet natural gas preparing synthetic gas be mixed for synthesizing methanol;
(3) utilization of unreacting gas: unreacted gas in step (2) the synthesizing methanol process is divided into three parts, first part of circulation is used for the synthesizing methanol of step (2), second part acts as a fuel and provides heat to gas renormalizing reaction, and the 3rd part is used for gas turbine power generation and heat supply;
(4) preparation of the preparation of alkene and ammonia: the methyl alcohol that step (2) is obtained is divided into two parts, and portion is used for preparing alkene and this process produces water; The water that produces in another part methyl alcohol and the preparation olefin hydrocarbon carries out reforming reaction, preparation hydrogen and carbonic acid gas, separating hydrogen gas and carbonic acid gas, the nitrogen that hydrogen that separation is obtained and air separation obtain is mixed for synthetic ammonia, separates the carbonic acid gas that obtains and is used for the gas renormalizing reaction.
2. method according to claim 1 is characterized in that, in the step (1), the coal gasification reaction condition is: pressure 0～10MPa, and 1000～1600 ℃ of temperature, and control that hydrogen-carbon ratio is 0.4～0.7 in the described producing synthesis gas from coal; Described gas renormalizing reaction conditions is 700～950 ℃ of pressure 1.0～2.5MPa, temperature, and is that hydrogen-carbon ratio is 3 in the Sweet natural gas preparing synthetic gas of raw material with water vapour, and carbonic acid gas is that hydrogen-carbon ratio is 1 in the Sweet natural gas preparing synthetic gas of raw material; The input quality of control raw natural gas and coal is 0～2.3, is preferably 2.3.
3. method according to claim 1 and 2 is characterized in that, in the step (1), the purifying treatment of described water-gas is for to reclaim the high temperature sensible heat with water-gas, and temperature is reduced to 40 ℃, and removes and deash, and carries out desulfurization then and handles, and further reclaims heat after the desulfurization; Preferred described desulfurization is treated to wet desulphurization, more preferably low-temperature rectisol method or polyglycol dimethyl ether process.
4. method according to claim 3 is characterized in that, after handling through described desulfurization, and water-gas total sulfur content≤10mg/Nm
3
5. method according to claim 1 is characterized in that, the described synthesizing methanol reaction conditions of step (2) is 200～300 ℃ of pressure 4～10MPa, temperature.
6. method according to claim 1 and 2 is characterized in that, first part of unreacted gas of step (3) carries out gas conversion through at pressure 5MPa under the condition that temperature is 250 ℃, and circulating then, it is synthetic to be used for methyl alcohol.
7. method according to claim 1, it is characterized in that the 3rd part of unreacting gas of step (3) is used for generating and heat supply is, unreacting gas is sent to the gas turbine combustion acting, high-temperature flue gas of discharging and boiler hot exchange produce hot steam, are used to drive steam turbine and heat supply.
8. method according to claim 1 is characterized in that, the condition of step (4) preparation alkene is 400～550 ℃ of pressure 0.2～0.5MPa, temperature, and sieves as catalyzer with the silicon aluminium phosphate molecules of salt.
9. method according to claim 1 is characterized in that, the described reforming reaction condition of step (4) is that temperature is 250～300 ℃, and pressure is 1～5MPa.
10. device that is used to realize each described method of claim 1～9, this device comprises:
Air separation plant, being used for air separation is oxygen and nitrogen;
Vapourizing furnace, the oxygen that is used to provide coal and water vapour, air separation to obtain carries out gasification reaction and obtains water-gas;
Refining plant, the coal gas that is used to purify waste water obtains producing synthesis gas from coal;
Reforming reactor is used to provide Sweet natural gas and carbonic acid gas to carry out reforming reaction and obtains the Sweet natural gas preparing synthetic gas;
Methanol synthesizer is used for producing synthesis gas from coal and Sweet natural gas preparing synthetic gas mixing synthesizing methanol; And this methanol synthesizer is provided with and is used for part unreacting gas in it is drawn methanol synthesizer is recycled into methanol synthesizer behind gas conversion pipeline; Also be provided with the part unreacting gas is drawn the pipeline that methanol synthesizer is sent to the reforming reaction device; Also be provided with the part unreacting gas is drawn the pipeline that methanol synthesizer is sent to power generation assembly;
Power generation assembly is used to accept the part unreacting gas from methanol synthesizer, by gas turbine power generation and heat supply;
The alkene synthesizer, being used for the methyl alcohol from methanol synthesizer is the synthetic alkene of raw material, and produces water;
The methanol recapitalization device, be used for being that raw material carries out reforming reaction and prepares hydrogen and carbonic acid gas from the methyl alcohol of methanol synthesizer and from the water of alkene synthesizer, and this device is provided with the equipment of separating hydrogen gas and carbonic acid gas, and is provided with the pipeline that carbonic acid gas is delivered to the gas renormalizing reactor;
Ammonia synthesizer is used to accept finish the ammonia synthesis reaction of hydrogen and nitrogen from the hydrogen of methanol recapitalization device and from the nitrogen of air separation plant.
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