CN108059977B

CN108059977B - Near zero emission and CO (carbon monoxide)2Resource utilization fossil energy utilization method

Info

Publication number: CN108059977B
Application number: CN201711408356.9A
Authority: CN
Inventors: 朱维群; 柴树; 王倩; 孟丽
Original assignee: Shandong University
Current assignee: Shandong University
Priority date: 2017-12-22
Filing date: 2017-12-22
Publication date: 2021-03-26
Anticipated expiration: 2037-12-22
Also published as: CN108059977A

Abstract

本发明涉及一种近零排放、CO₂资源化利用的化石能源利用方法，本发明方法将煤气化、发电与化学产品生产耦合起来，耦合过程中将各过程物流、能量进行整合，即：从持续排放的CO₂中取一定量输入发电系统循环利用，发电产生的水或蒸汽作流化气参与气化反应，其余CO₂作为化工原料生产1,3,5‑均三嗪三醇，将1,3,5‑均三嗪三醇化学产品的化工生产和发电有机的结合起来，从根本上解决了CO₂循环使用和C原子的充分利用，实现CO₂的零排放。解决了现有多联产工艺中大量排放CO₂温室气体的关键技术，实现了CO₂资源化利用、绿色能源和化学工业的目的。实现CO₂和氢气高效有机利用，该方法可以同时实现SO₂、NO_X、颗粒物及CO₂近零排放，而且降低H₂发电风险并实现CO₂资源化利用的方法。The invention relates to a fossil energy utilization method with near zero emission and CO ₂ resource utilization. The method of the invention couples coal gasification, power generation and chemical product production, and integrates the logistics and energy of each process during the coupling process, that is: from A certain amount of continuously emitted _CO2 is input into the power generation system for recycling, the water or steam generated by power generation is used as fluidizing gas to participate in the gasification reaction, and the remaining _CO2 is used as chemical raw material to produce 1,3,5-s-triazine triol, which will The organic combination of chemical production of 1,3,5‑s-triazinetriol chemical products and power generation fundamentally solves the problem of CO ₂ recycling and full utilization of C atoms, and achieves zero CO ₂ emissions. It solves the key technology of massive emission of _CO2 greenhouse gas in the existing polygeneration process, and realizes the purpose of _CO2 resource utilization, green energy and chemical industry. To achieve efficient organic utilization of CO ₂ and hydrogen, the method can simultaneously achieve near-zero emissions of SO ₂ , NO _X , particulate matter and CO ₂ , reduce the risk of H ₂ power generation, and realize the method of CO ₂ resource utilization.

Description

Near zero emission and CO (carbon monoxide)2Resource utilization fossil energy utilization method

Technical Field

The invention relates to near zero emission and CO₂A resource utilization fossil energy utilization method belongs to the technical field of coal combustion environmental protection.

Background

Fossil energy accounts for 85% of primary energy in China, and coal accounts for the highest percentage, namely about 66%. The heavy use of fossil energy leads to SO₂、NO_XParticulate matter and CO₂And the quality of the atmospheric environment is sharply deteriorated. Although pollution can be reduced by removing various pollutants after combustion; but requires a large investment in equipment and produces a large amount of CO₂。CO₂The emission of the carbon dioxide not only aggravates the greenhouse effect to cause global climate change, but also causes waste of carbon resources. Hydrogen energy has received much attention because of its high energy density, high thermal conversion efficiency, and the combustion products only containing water. Natural gas or coke oven gas is good in economy, and the extraction rate and purity of hydrogen are high (see the current research situation and development prospect of hydrogen production technology, modern chemical engineering, 2013,33(5):31-35), and the natural gas or coke oven gas is often used as fossil fuel suitable for industrial large-scale hydrogen production; such as: integrated coal gasification gas steamThe gas combined cycle power generation system (IGCC) is clean and efficient, and can realize CO₂Near zero emission (see IGCC polygeneration system route selection research, northeast electric technology 2014,35(8): 22-25); but does not solve the problems of high risk and CO in pure hydrogen power generation₂Resource utilization and the like.

The pure hydrogen is easy to explode during combustion, and simultaneously generates the conditions of higher NOx emission and the like, and at present, hydrocarbon fuel or nitrogen is mainly mixed for combustion. At present, CO₂The research of resource utilization mainly aims at synthesizing methane, methanol, dimethyl ether or liquid fuel and the like, and the main problem is H₂The dosage is large, the energy consumption of the process is high, and the life cycle of the product is short.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a near zero emission CO preparation method₂A method for utilizing fossil energy for resource utilization.

Summary of the invention:

the method of the invention couples coal gasification, power generation and chemical product production, and integrates material flow and energy of each process in the coupling process, namely: from continuously emitted CO₂A certain amount of water or steam generated by power generation is taken as fluidizing gas to participate in gasification reaction, and the rest of CO is recycled₂The 1,3, 5-s-triazine triol is produced as a chemical raw material, and the chemical production and the power generation of the chemical product of the 1,3, 5-s-triazine triol are organically combined, so that the problem of CO is fundamentally solved₂Cyclic utilization and full utilization of C atom to realize CO₂Zero emission of (2). Solves the problem of large emission of CO in the prior poly-generation process₂The key technology of greenhouse gas realizes CO₂Resource utilization, green energy and chemical industry. Realization of CO₂And hydrogen gas are efficiently and organically utilized, and the method can simultaneously realize SO₂、NO_XParticulate matter and CO₂Near zero emission and H reduction₂Risk of power generation and CO realization₂A method for resource utilization.

The invention is realized by the following technical scheme:

near zero emission and CO (carbon monoxide)₂Resource utilization fossil energy resourceBy means of CO produced in the process₂As raw material for the production of chemicals, together with a certain amount of CO₂The power is transmitted back to the power generation system for recycling, and no CO exists in the whole process₂Discharging outwards; the method comprises the following steps:

(1) the method comprises the following steps of (1) taking water vapor as fluidized gas, carrying out gasification reaction on the fossil fuel under the conditions of pressure of 1-10 Mpa and temperature of 1200-1600 ℃ to obtain crude reformed gas, and carrying out transformation reaction on the crude reformed gas under the conditions of pressure of 1-10 Mpa and temperature of 180-460 ℃ to obtain crude transformed gas;

(2) the high-purity hydrogen is obtained by desulfurizing and decarbonizing the crude shift gas, and then CO is carried out₂High purity CO is obtained by resolution₂；

(3) High purity CO obtained in step (2)₂And taking hydrogen and CO accounting for 20-50% of the total hydrogen in the high-purity hydrogen₂The diluted gas is input into a power generation system, and simultaneously oxygen is input to be mixed to carry out combustion power generation and simultaneously generate water and CO₂The input quantity is used for diluting the hydrogen concentration to 20-60%;

(4) step (2) high purity CO₂And high purity hydrogen, with the remainder being any CO that is continuously produced₂50-80% of hydrogen and N obtained by air separation₂Synthesizing a solid product 1,3, 5-s-triazine triol;

(5) residual CO of power generation₂All the water or steam is returned to the power generation system for recycling, and the generated water or steam is used as the fluidizing gas in the step (1) to participate in the gasification reaction.

Preferably, according to the present invention, the gasification reaction in step (1) is performed in a gasifier, which is a fixed bed/moving bed gasifier, a fluidized bed/fluidized bed gasifier or an entrained flow gasifier, the fixed bed/moving bed gasifier is a UGI furnace, a Lurgi (Lurgi) furnace or a slag tapping Lurgi (BGL) furnace, the fluidized bed/fluidized bed gasifier is a circulating fluidized bed gasifier or a bubbling fluidized bed gasifier, and the entrained flow gasifier is a Texaco, shell or GSP gasifier.

Preferably according to the invention, the shift reaction of step (1) is carried out in a shift converter, which is a shaft shift or tubular temperature shift converter.

Step (1) of the present invention is carried out according to the prior art, see the comparison of coal gasification processes in the literature, Zhongzi N fertilizer 2001, (1): 30-32.

According to the present invention, the desulfurization and decarburization step in step (2) is preferably a low-temperature methanol washing step, a dimethyl ether polyethylene glycol (Selexol) step, or a MEDA step.

The desulfurization and decarbonization of the step (2) of the invention are carried out according to the prior art, see selection and comparison of coal gasification purification technology, chemical engineering and equipment, 2009, (1), 108-.

Preferably, according to the present invention, in the step (3), CO is combusted at the time of power generation₂、H₂、O₂The flow ratio is 0.1-2.3: 1: 0.5-0.6, and the fuel-air equivalence ratio phi is 0.8-1.4.

According to the present invention, in the step (3), N obtained by partially separating air is preferably introduced during combustion power generation₂，CO₂、N₂、H₂、 O₂The flow ratio is 0.2-1.3: 0.1-1: 1: 0.5-0.6, and the fuel-air equivalence ratio phi is 0.8-1.4.

Preferably, in step (3), the power generation system is a gas turbine and a steam turbine of a power station.

According to the invention, in step (4), the solid product 1,3, 5-s-triazine triol is synthesized as CO₂、H₂、N₂The volume ratio is 1: 1.5-1.7: 3.0-3.4.

According to the present invention, in step (4), the specific conditions for synthesizing the solid product 1,3, 5-s-triazine triol are as follows: n is a radical of₂And H₂Firstly, NH is synthesized under the conditions of 15-20 MPa and 400-520 DEG C₃Then NH₃With CO₂Firstly synthesizing urea liquid under the conditions of 10-30 MPa and 185-190 ℃, and finally synthesizing a solid product 1,3, 5-s-triazine triol from the urea liquid at 150-350 ℃ and 1-10 MPa, and simultaneously releasing NH₃Returning to continue utilization, the reactor can be a microwave reactor or a spiral tube reactor, and the catalyst is ammonium chloride.

The invention has the advantages that the energy utilization rate is improved by hydrogen production and combustion from fossil energy, and SO is realized₂、NO_XParticulate matter and CO₂Near zero emission; CO produced₂Only a small amount ofHydrogen and readily available N₂To synthesize CO₂The highest content of stable solid product; hydrogen in CO₂The power generation under dilution reduces the combustion risk and CO₂The cyclic utilization does not need to be supplemented; h₂The water generated by combustion can be returned to the hydrogen production process again, and the energy consumption and the water consumption of the whole process are reduced.

Compared with the prior art, the invention has the beneficial effects that: the energy utilization rate is improved, the emission of pollutants and greenhouse gas is reduced, and the high-value utilization of carbon resources is realized.

Drawings

FIG. 1 is a diagram of a near zero emission, CO system according to the present invention₂A flow diagram of a fossil energy utilization method for resource utilization.

Detailed Description

In order to further understand the present invention, the following will explain the simple and efficient method for utilizing fossil energy provided by the present invention in detail with reference to the following embodiments.

Example 1

Near zero emission and CO (carbon monoxide)₂Resource utilization fossil energy utilization method and CO generated in process₂Synthesis of chemicals, a certain amount of CO₂The power is transmitted back to the power generation system for cyclic use, and the whole process has no CO₂Discharging outwards; the method comprises the following steps:

(1)1000 tons of lignite (2.03 percent of sulfur) take water vapor as fluidized gas, gasification reaction is carried out under the conditions of pressure intensity of 9.3Mpa and temperature of 1350 ℃ to obtain crude conversion gas, and the crude conversion gas is subjected to shift reaction under the conditions of pressure intensity of 6.5Mpa and temperature of 230 ℃ to obtain crude conversion gas;

(2) the crude shifted gas was subjected to a low-temperature methanol washing step to obtain about 165 tons of high-purity hydrogen gas having a concentration of 99.5%, and then subjected to reduced-pressure desorption to obtain about 1076 tons of high-purity CO having a concentration of 99.1%₂；

(3) High purity CO₂And taking 92 tons of hydrogen and 1 ton of CO in the high-purity hydrogen₂Maintaining hydrogen and CO at the inlet₂The coal enters a solar Samsung 20 gas turbine for combustion power generation under the condition of a flow ratio of about 1:1.5, 220MWh electricity is generated, and about 820 tons of water vapor are generated at the same time;

(4) high purity CO₂And 1075 tons of CO in the high purity hydrogen gas₂And 73 tons of hydrogen, together with N obtained by air separation₂About 1040 tons of white solid product 1,3, 5-s-triazine triol with the purity of 92.3 percent is synthesized;

(5) CO in the process of power generation₂The water or steam generated by combustion is used as the fluidizing gas in the step (1) to participate in the gasification reaction.

Example 2

Near zero emission and CO (carbon monoxide)₂Utilization method of fossil energy for resource utilization, synthesis of chemicals and a certain amount of CO₂The power is transmitted back to the power generation system, and the whole process has no CO₂Discharging outwards; the method comprises the following steps:

(1)1500 tons of lignite (2.10 percent of sulfur content) take water vapor as fluidized gas, gasification reaction is carried out under the conditions of 8.5Mpa of pressure and 1330 ℃ of temperature to obtain crude converted gas, and the crude converted gas is subjected to shift reaction under the conditions of 6.5Mpa of pressure and 240 ℃ of temperature to obtain crude shifted gas;

(2) the crude shift gas is subjected to a low-temperature methanol washing process to obtain 248 tons of high-purity hydrogen with the concentration of 99.4 percent, and then the high-purity CO with the concentration of 99.1 percent is obtained by decompression and analysis to obtain 1600 tons of high-purity CO with the concentration of 99.1 percent₂；

(3) High purity CO₂And taking 148 tons of hydrogen and 2 tons of CO from the high-purity hydrogen₂Maintaining hydrogen and CO at the inlet₂The gas enters a solar Samsung 20 gas turbine for combustion power generation under the condition of a flow ratio of about 1:1.7, 350MWh electricity is generated, and meanwhile about 1320 tons of water vapor are generated;

(4) high purity CO₂And in the high purity hydrogen, the total remaining 1598 tons of CO₂And 110 tons of hydrogen, with N obtained by air separation₂1566 tons of white solid product 1,3, 5-s-triazine triol with the purity of 91.3 percent is synthesized;

Comparative example 1

Near zero emission and CO (carbon monoxide)₂Resource utilizationA fossil energy utilization process carried out as in example 1 except that:

step (3) taking hydrogen and CO accounting for 10 percent of the total hydrogen₂The diluted gas is input into a power generation system, and simultaneously oxygen is input to be mixed to carry out combustion power generation and simultaneously generate water and CO₂The input quantity is used for diluting the hydrogen concentration to 20-60%;

step (4) high purity CO₂And high purity hydrogen, with the remainder being any CO that is continuously produced₂And 90% hydrogen with N obtained by air separation₂The synthesis of the solid product 1,3, 5-s-triazine triol, the electricity production and the yield of the 1,3, 5-s-triazine triol are compared with the invention.

Comparative example 2

Near zero emission and CO (carbon monoxide)₂The fossil energy utilization method for resource utilization was carried out in the same manner as in example 1, except that:

step (3) taking hydrogen and CO accounting for 90 percent of the total hydrogen₂、N₂The diluted gas is input into a power generation system, and simultaneously oxygen is input to be mixed to carry out combustion power generation and simultaneously generate water and CO₂、N₂The flow ratio is 1:1, and the total input amount enables the concentration of hydrogen to be diluted to 20-60%;

step (4) high purity CO₂And high purity hydrogen, with the remainder being any CO that is continuously produced₂And 10% hydrogen with N obtained by air separation₂The synthesis of the solid product 1,3, 5-s-triazine triol, the electricity production and the yield of the 1,3, 5-s-triazine triol are compared with the invention.

Experimental example:

taking the Zhuang coal as an example, the Zhuang coal is one of common coal types, has high carbon content and low hydrogen content, and the elemental analysis of the Zhuang coal is as follows:

TABLE 1

	C	H	N	S	O
						Coal as one kind	55.44	2.74	0.73	1.1	3.4

Methods of examples 1-2 and comparative examples 1-2: the effect of different gas distribution on product yield and power generation is shown in table 2:

TABLE 2

	Yield of 1,3, 5-s-triazinetriol	Total generated energy MW
			Example 1	85％	115.41
Example 2	80％	116.77
			Comparative example 1	58％	88.23
Comparative example 2	63％	71.34

As can be directly seen from the comparison in Table 2, the different proportion distribution of the gas directly causes the reduction of the yield and the power generation amount of the 1,3, 5-s-triazine triol, and the unreasonable distribution of the gas in the coupling process to CO₂Cyclic use and insufficient utilization of C atoms, CO₂During the coupling process, it is discharged to the environment, resulting in the loss of C.

Claims

1. A fossil energy utilization method with near zero emission and CO ₂ resource utilization. CO ₂ generated in the process is used as raw material to produce chemicals, and a certain amount of CO ₂ is returned to the power generation system for recycling, and there is no CO ₂ in the whole process. Emissions; including steps as follows:

(1) Fossil fuels use water vapor as the fluidizing gas, and carry out gasification reaction at a pressure of 1-10Mpa and a temperature of 1200-1600℃ to obtain crude reformed gas. The crude reformed gas is at a pressure of 1-10Mpa, 180- Carry out the shift reaction under the temperature of 460°C to obtain the crude shift gas; the gasifier is a fixed bed/moving bed gasifier, a fluidized bed/fluidized bed gasifier or an entrained bed gasifier, the fixed bed/moving bed gasifier The gasifier is a UGI furnace, a Lurgi furnace or a BGL furnace, and the fluidized bed/fluidized bed gasifier is a circulating fluidized bed gasifier or a bubbling fluidized bed gasifier , the entrained-flow gasifier is Texaco, shell or GSP gasifier; the shift reaction is carried out in a shift furnace, and the shift furnace is an axial meridian shift or a tubular temperature shift furnace;

(2) The crude shift gas is desulfurized and decarbonized to obtain high-purity hydrogen, and then subjected to CO ₂ analysis to obtain high-purity CO ₂ ; the desulfurization and decarbonization processes are low-temperature methanol washing process, polyethylene glycol dimethyl ether method (Selexol) process, MEDA process;

(3) Among the high-purity CO ₂ and high-purity hydrogen obtained in step (2), hydrogen and CO ₂ , which account for 20-50% of the total hydrogen, are taken as diluent gas and input into the power generation system, and at the same time, oxygen is mixed for combustion and power generation. Water is produced, and the input of CO ₂ dilutes the hydrogen concentration to 20~60%; the flow ratio of CO ₂ , H ₂ , and O ₂ is 0~2.3:1:0.5~0.6 during combustion and power generation, and the fuel-air equivalent ratio is φ=0.8~1.4 ; Or the N ₂ , CO ₂ , N ₂ , H ₂ , O ₂ flow ratio obtained by inputting part of the air separation during combustion power generation is 0.2~1.3:0.1~1:1:0.5~0.6, and the fuel-air equivalent ratio is φ=0.8~ 1.4; The power generation system is a power station gas turbine and a steam turbine;

(4) Step (2) Among the high-purity CO ₂ and high-purity hydrogen, the remaining CO ₂ and 50~80% hydrogen that are continuously produced are combined with the N ₂ obtained by air separation to synthesize the solid product 1,3,5-homostri azine triol; the volume ratio of CO ₂ , H ₂ and N ₂ in the synthetic solid product 1,3,5-s-triazine triol is 1:1.5~1.7: 3.0~3.4; the synthetic solid product 1,3,5-homogeneous The specific conditions of triazine triol are as follows: N2 and H2 first synthesize NH ₃ under the conditions of 15~20MPa and 400℃~520℃, and then _NH3 and CO ₂ first synthesize urea liquid under the conditions of 10~30MPa and 185~190℃ , and finally the urea liquid is at 150~350℃, 1~10Mpa to synthesize the solid product 1,3,5-s-triazine triol, and the _NH3 released at the same time is returned to continue to be used, and the reactor can be a microwave reactor, a spiral tube reactor , the catalyst is ammonium chloride;

(5) All the remaining CO ₂ in power generation is returned to the power generation system for recycling, and the produced water or steam is used as the fluidizing gas in step (1) to participate in the gasification reaction.