TWI617508B - Biogas catalyst cogeneration unit and operation method thereof - Google Patents

Biogas catalyst cogeneration unit and operation method thereof Download PDF

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TWI617508B
TWI617508B TW105138069A TW105138069A TWI617508B TW I617508 B TWI617508 B TW I617508B TW 105138069 A TW105138069 A TW 105138069A TW 105138069 A TW105138069 A TW 105138069A TW I617508 B TWI617508 B TW I617508B
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catalyst
biogas
reforming reactor
storage tank
gas
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TW201819285A (en
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Heng-Xin Huang
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Huang Heng Xin
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E20/00—Combustion technologies with mitigation potential
    • Y02E20/14—Combined heat and power generation [CHP]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/10—Biofuels, e.g. bio-diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E50/00—Technologies for the production of fuel of non-fossil origin
    • Y02E50/30—Fuel from waste, e.g. synthetic alcohol or diesel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/20—Waste processing or separation

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Abstract

本發明係提供一沼氣觸媒熱電共生機，可自動操作提供日常生活所需的熱氣、熱水及電的分散式能源供應機，其包含：一沼氣儲存槽；一觸媒重整反應器，其包含顆粒狀受載型或非受載型鉑族金屬觸媒，且與該沼氣儲存槽相連接；一氧氣儲存槽，與該觸媒重整反應器相連接；一重整氣儲存槽，與該觸媒重整反應器相連接；及一自動控制系統，其包含控制電腦和/或微處理器、流量計/控制器、閥門、泵、傳感器、溫度計、操作的控制軟體，使沼氣儲存槽及該氧氣儲存槽提供在該觸媒重整反應器入口處的氧氣、水和沼氣之燃料混合氣，並保持O2/CH4比例在0.8以下，且(H2O+CO2)/CH4比例在10.0以下。 The present invention provides a biogas catalyst cogeneration unit that can automatically operate a decentralized energy supply machine that provides hot gas, hot water, and electricity for daily life. It includes: a biogas storage tank; and a catalyst reforming reactor. It contains a granular supported or unsupported platinum group metal catalyst and is connected to the biogas storage tank; an oxygen storage tank is connected to the catalyst reforming reactor; a reformed gas storage tank, Connected to the catalyst reforming reactor; and an automatic control system including control computer and / or microprocessor, flow meter / controller, valve, pump, sensor, thermometer, and operation control software to enable biogas storage The tank and the oxygen storage tank provide a fuel mixture of oxygen, water and biogas at the entrance of the catalyst reforming reactor, and keep the O 2 / CH 4 ratio below 0.8, and (H 2 O + CO 2 ) / The CH 4 ratio is below 10.0.

Description

沼氣觸媒熱電共生機及其操作方法 Biogas catalyst cogeneration unit and operation method thereof

本發明係關於一種沼氣觸媒熱電共生機及其操作方法。 The invention relates to a biogas catalyst cogeneration machine and an operation method thereof.

大自然空氣中的CO2可藉由光合作用被植物轉換成糖、澱粉、草、藻類、菜、樹葉或水果等動物的食物。若食物經動物消化後，其***物或剩餘的廚房及農產品等有機廢棄物，便可經由厭氧醱酵槽來產生沼氣。厭氧醱酵槽是將動物消化後的***物，以及剩餘的有機廢棄物，經由酵母在大約38℃無氧醱酵後，來產生含硫化物並俱有臭味的沼氣，以及除臭味後的有機水及固體肥料。一般而言，沼氣含有55-60%甲烷(CH4)、40-45%二氧化碳(CO2)、0.4-1.2%氮(N2)、0.0-0.4%(O2)和0.02-0.4%硫化氫(H2S)。 CO 2 in nature's air can be converted into sugar, starch, grass, algae, vegetables, leaves or fruits by animals through photosynthesis. If the food is digested by animals, its waste or organic waste such as kitchen and agricultural products can pass through the anaerobic fermentation tank to produce biogas. The anaerobic fermentation tank is the excrement after digestion of animals and the remaining organic waste. After anaerobic fermentation by yeast at about 38 ° C, sulfide-containing biogas with odor and deodorization are produced. After the organic water and solid fertilizer. Generally speaking, biogas contains 55-60% methane (CH 4 ), 40-45% carbon dioxide (CO 2 ), 0.4-1.2% nitrogen (N 2 ), 0.0-0.4% (O 2 ), and 0.02-0.4% sulfur Hydrogen (H 2 S).

已知純化後之沼氣可用於汽電共生系統。沼氣技術除收集沼氣內可利用60%至80%甲烷當能源外，尚需有脫硫技術，來避免沼氣中的硫化物對下游設備的腐蝕，以大幅提升沼氣利用率，並降低溫室氣體排放量，或形成可燃的H2和CO重整氣。 It is known that the purified biogas can be used in a cogeneration system. In addition to collecting 60% to 80% of methane in biogas as energy source, biogas technology also needs desulfurization technology to avoid the corrosion of downstream equipment by sulfide in biogas, in order to greatly improve the utilization of biogas and reduce greenhouse gas emissions. amount or form a combustible reformed gas CO and H 2.

在1970年代的石油危機，美國開始研發分散式觸媒產氫的自熱重整反應器，來供應氫氣給使用燃料電池的熱電共生機使用。在研發觸媒重整反應器的初期，是使用顆粒狀的無機氧化物做為燃料部份氧化反應的觸媒劑，將燃料轉化成氫氣，同時也供應熱能給下游的蒸氣重整觸媒劑， 繼續將未反應的燃料轉化成氫氣。在1980年代，US 4,522,894中揭示首次使用整體Pt/Pd/Al2O3做部份氧化反應的觸媒劑，來從商業用含硫的柴油製造H2和CO，並供應熱能給下游的顆粒狀Ni/Al2O3或Pt/Pd/Al2O3觸媒劑，做蒸氣重整產氫的反應。由於Pt/Pd/Al2O3觸媒劑有極快速的反應速度及極佳的選擇性，觸媒重整反應器入口的氧氣能在低於36毫秒(在標準溫壓下，空間速度>100,000/hr)內完全反應。被反應的柴油也大部份轉換成H2和CO，而不是經由完全燃燒反應所產生無法做為燃料電池燃料的H2O和CO2。因此，整體Pt/Pd/Al2O3是個極佳的部份氧化反應觸媒劑。其後，在2000年代研發由天然煤氣、其他碳氫化合物或生質燃料來產氫時，也發現顆粒狀受載型或非受載型的鉑族金屬觸媒(supported or unsupported Pt metal group)，其皆為良好的部分氧化觸媒劑。即包含一種或多種諸如鉑(Pt)、鈀(Pd)、銠(Rh)、銥(Ir)、鋨(Os)、釕(Ru)的鉑族金屬觸媒，都可以成功並快速的將碳氫化合物或生質燃料轉化成H2和CO的重整氣，並俱有極佳的選擇性(>93% selectivity)。 During the oil crisis of the 1970s, the United States began to develop a self-heating reforming reactor for decentralized catalyst hydrogen production to supply hydrogen for use in thermoelectric cogeneration machines using fuel cells. In the early stage of the development of a catalytic reforming reactor, particulate inorganic oxides were used as catalysts for the partial oxidation reaction of the fuel to convert the fuel into hydrogen, while also supplying thermal energy to the downstream steam reforming catalyst. Continue to convert unreacted fuel into hydrogen. In the 1980s, US 4,522,894 revealed that for the first time a catalyst for partial oxidation of Pt / Pd / Al 2 O 3 as a whole was used to produce H 2 and CO from commercial sulfur-containing diesel and to supply heat to downstream particles. Ni / Al 2 O 3 or Pt / Pd / Al 2 O 3 catalysts are used to produce hydrogen by steam reforming. Due to the extremely fast reaction speed and excellent selectivity of the Pt / Pd / Al 2 O 3 catalyst, the oxygen at the inlet of the catalyst reforming reactor can be below 36 milliseconds (at standard temperature and pressure, the space velocity> 100,000 / hr). Most of the reacted diesel is also converted into H 2 and CO, instead of H 2 O and CO 2 produced by the complete combustion reaction, which cannot be used as fuel cell fuel. Therefore, the overall Pt / Pd / Al 2 O 3 is an excellent catalyst for partial oxidation reaction. Later, during the development of hydrogen from natural gas, other hydrocarbons, or biomass fuels in the 2000s, particulate supported or unsupported platinum group metal catalysts were also found (supported or unsupported Pt metal group). They are all good partial oxidation catalysts. That is, one or more platinum group metal catalysts such as platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), osmium (Os), and ruthenium (Ru) can successfully and quickly convert carbon. Hydrogen compounds or biomass fuels are converted into reformed gas of H 2 and CO with excellent selectivity (> 93% selectivity).

目前人類生活與工作對於電能的依賴日益提高，而高效率的集中發電方式環境成本高，且在能源運輸的過程可能造成損失。因此，本發明的主要目的為提供一種利用沼氣、生質燃料或碳氫化合物等進行發電，並同時利用過程中所產生的熱能之分散式能源供應機。其可以避免或降低因長途輸電之電力損失，也可以有效的供應熱能給附近的居民或公司作為日常生活的必需品，利用沼氣發電所產生的熱能和電能是一種具有降低碳排放量功效的技術。 At present, human life and work are increasingly dependent on electrical energy, and high-efficiency centralized power generation methods have high environmental costs and may cause losses in the process of energy transportation. Therefore, the main object of the present invention is to provide a decentralized energy supply machine that uses biogas, biomass fuels, or hydrocarbons to generate electricity and simultaneously uses the thermal energy generated in the process. It can avoid or reduce power loss due to long-distance power transmission, and can also effectively supply thermal energy to nearby residents or companies as a necessity of daily life. The use of heat and electricity generated by biogas power generation is a technology with the effect of reducing carbon emissions.

US 9,440851，其內容皆以參考方式併入本文中，其係與本 案為同一發明人，其描述一部最新研發的車載觸媒產氫觸媒重整反應器，此觸媒重整反應器可以提供一些設備和自動操作這些裝置的方法，能將所有可揮發的碳氫化合物或生質物，經過此觸媒產氫觸媒重整反應器後，在沒有外部而只利用本身所產生熱量和電力的供應下，利用Pt組金屬催化劑，來產生含H2和CO的可燃燒重整氣。而本專利是設計一部機器，利用觸媒催化反應，使用二階段重整器，一除硫吸附器和使用不同操作的條件下，將沼氣燃料中的硫化物脫(除)硫並產生可燃的H2和CO重整氣。因此，此种由異質(heterogeneous)觸媒反應方式所產生的重整氣，與由固體生質物經過同質(homogeneous)反應方式所產生的重整氣，在設備和生產的程序上是有明顯的差異。 US 9,440851, the content of which is incorporated herein by reference. It is the same inventor as this case. It describes a newly developed vehicle-mounted catalyst hydrogen production catalyst reforming reactor. This catalyst reforming reaction The reactor can provide some equipment and a method for automatically operating these devices. It can reform all reactors that use volatile hydrocarbons or biomass through this catalyst to produce hydrogen and use only the heat generated by itself without the outside. With the supply of electricity and Pt metal catalysts, a combustible reformed gas containing H 2 and CO is produced. This patent is to design a machine that uses a catalyst to catalyze the reaction, uses a two-stage reformer, a desulfurization adsorber, and uses different operating conditions to desulfurize (desulfurize) the biogas fuel and generate flammable fuel. H 2 and CO reformed gas. Therefore, the reformed gas generated by a heterogeneous catalyst reaction method and the reformed gas generated by a solid biomass through a homogeneous reaction method are obvious in equipment and production procedures. difference.

本發明之一主要目的在於一種沼氣觸媒熱電共生機，其包含：一沼氣儲存槽；一觸媒重整反應器，其包含顆粒狀受載型或非受載型鉑族金屬觸媒，且與該沼氣儲存槽相連接；；一重整氣儲存槽，與該觸媒重整反應器相連接；及一自動控制系統，其包含控制電腦和/或微處理器、流量計/控制器、閥門、泵、傳感器、溫度計、操作的控制軟體，使沼氣儲存槽及該氧氣儲存槽提供在該觸媒重整反應器入口處的氧氣、水和沼氣之燃料混合氣，並保持O2/CH4比例在0.8以下，且(H2O+CO2)/CH4比例在10.0以下。 One of the main objects of the present invention is a biogas catalyst thermoelectric symbiosis machine, comprising: a biogas storage tank; a catalyst reforming reactor comprising a particulate supported or unsupported platinum group metal catalyst, and Connected to the biogas storage tank; a reformed gas storage tank connected to the catalyst reforming reactor; and an automatic control system including a control computer and / or microprocessor, a flow meter / controller, Valves, pumps, sensors, thermometers, and operating control software enable the biogas storage tank and the oxygen storage tank to provide a fuel mixture of oxygen, water, and biogas at the entrance of the catalyst reforming reactor, and maintain O 2 / CH The ratio of 4 is 0.8 or less, and the ratio of (H 2 O + CO 2 ) / CH 4 is 10.0 or less.

於一較佳實施態樣中，該重整氣儲存槽下方連接一內燃機/渦輪機。 In a preferred embodiment, an internal combustion engine / turbine is connected below the reformed gas storage tank.

於一較佳實施態樣中，觸媒重整反應器包含至少一個蒸汽重整反應器、部分氧化重整反應器或自熱重整反應器，且該鉑族金屬觸媒為包含一種或 多種選自由鉑(Pt)、鈀(Pd)、銠(Rh)、銥(Ir)、鋨(Os)及釕(Ru)所組成之群組之金屬，其為含有總鉑族金屬在0.10至2000g/ft3之間的顆粒狀受載型或非受載型鉑族金屬觸媒。 In a preferred embodiment, the catalyst reforming reactor includes at least one steam reforming reactor, partial oxidation reforming reactor, or autothermal reforming reactor, and the platinum group metal catalyst includes one or more A metal selected from the group consisting of platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), osmium (Os), and ruthenium (Ru), which contains 0.10 to 2000 g of a total platinum group metal / ft 3 Particulate supported or unsupported platinum group metal catalyst.

於一較佳實施態樣中，該沼氣儲存槽係先與一乾燥及吸附槽連接後，再連接至觸媒重整反應器。 In a preferred embodiment, the biogas storage tank is first connected to a drying and adsorption tank, and then connected to the catalyst reforming reactor.

於一較佳實施態樣中，該乾燥及吸附槽係進一步與一啟動IC引擎及發電機連接，且該啟動IC引擎及發電機連接亦與該觸媒重整反應器連接。 In a preferred embodiment, the drying and adsorption tank is further connected to a start-up IC engine and generator, and the start-up IC engine and generator are also connected to the catalyst reforming reactor.

於一較佳實施態樣中，該沼氣觸媒熱電共生機進一步包含一電解槽，該電解槽與一氫氣儲存槽及該氧氣槽連接，且該氫氣儲存槽與該啟動IC引擎及發電機連接。 In a preferred embodiment, the biogas catalyst cogeneration unit further includes an electrolytic cell, the electrolytic cell is connected to a hydrogen storage tank and the oxygen tank, and the hydrogen storage tank is connected to the start-up IC engine and generator .

於一較佳實施態樣中，該沼氣觸媒熱電共生機進一步包含一熱交換器，設置於該觸媒重整反應器及該重整氣儲存槽之間。 In a preferred embodiment, the biogas catalyst cogeneration unit further includes a heat exchanger disposed between the catalyst reforming reactor and the reforming gas storage tank.

於一較佳實施態樣中，其中該觸媒重整反應器內包含一硫化氫吸附劑。 In a preferred embodiment, the catalyst reforming reactor includes a hydrogen sulfide adsorbent.

本發明另一方面係提供一種操作本發明之沼氣觸媒熱電共生機之方法，其包含：提供一條或多條儲存在該控制電腦和/或該微處理器內的流量控制曲線，並依據各儲存槽內的氣壓來調節流量，使沼氣儲存槽及該氧氣儲存槽提供在該觸媒重整反應器入口處的氧氣、水和沼氣之燃料混合氣，保持O2/CH4比例在0.8以下，且(H2O+CO2)/CH4比例在10.0以下。 Another aspect of the present invention is to provide a method for operating the biogas catalyst cogeneration unit according to the present invention, comprising: providing one or more flow control curves stored in the control computer and / or the microprocessor, and according to each The air pressure in the storage tank is used to adjust the flow rate so that the biogas storage tank and the oxygen storage tank provide a fuel gas mixture of oxygen, water and biogas at the entrance of the catalyst reforming reactor, keeping the O 2 / CH 4 ratio below 0.8. And the (H 2 O + CO 2 ) / CH 4 ratio is below 10.0.

於一較佳實施態樣中，該操作方法進一步包含觸媒產氫觸媒重整反應器之三階段反應：第一階段，控制O2/CH4在0.08到0.25之間，觸媒 重整反應器溫度在200℃到500℃之間，且在含0-5%(H2+水蒸氣)的情況下，將沼氣內所有的硫化合物在經過顆粒狀受載型或非受載型鉑族金屬觸媒時，全部轉化為硫化氫；第二階段，利用一種或多種選自由鋅、鎳、銅、鈷、沸石、鐵、鋁、銅及鋅氧化物所組成之群組或混合氧化物做為硫化氫的吸附劑，並在200-500℃之間脫硫；及第三階段，利用第二階段的觸媒重整反應器，控制氧氣含量以提高O2/CH4比例，並提高沼氣中甲烷的反應轉換率和出口重整氣的產量。 In a preferred embodiment, the operation method further includes a three-stage reaction of a catalyst hydrogen-producing catalyst reforming reactor. In the first stage, O 2 / CH 4 is controlled between 0.08 and 0.25, and the catalyst is reformed. The reactor temperature is between 200 ° C and 500 ° C, and in the case of 0-5% (H 2 + water vapor), all sulfur compounds in the biogas are subjected to particulate supported or unsupported platinum In the case of a group metal catalyst, all of them are converted into hydrogen sulfide. In the second stage, one or more oxides selected from the group consisting of zinc, nickel, copper, cobalt, zeolite, iron, aluminum, copper, and zinc oxide are used. As an adsorbent for hydrogen sulfide, and desulfurized between 200-500 ° C; and in the third stage, the catalyst reforming reactor in the second stage is used to control the oxygen content to increase the O 2 / CH 4 ratio and increase Reaction conversion rate of methane in biogas and output of reformate gas.

於一較佳實施態樣中，其中第一階段係降低水蒸氣的含量來增加下游硫化氫的吸附劑吸附總量，以及利用氫和氧的反應熱來增加觸媒的溫度，並增加硫化合物和甲烷的觸媒部分氧化反應速度。 In a preferred embodiment, the first stage is to reduce the content of water vapor to increase the total amount of adsorbent adsorbed by downstream hydrogen sulfide, and use the reaction heat of hydrogen and oxygen to increase the temperature of the catalyst and increase the sulfur compounds. The rate of partial oxidation reaction with the catalyst of methane.

本發明相較於先前技術，提供了下列優勢：利用廚餘或***物經厭氧發酵生成之沼氣作為燃料，其是一種具有降低碳排放量功效的技術；簡化US 9,440,851揭示之車載燃料觸媒產氫觸媒重整反應器，重新設計為二階段重整器及增加一個脫硫吸附器，並調整其操作參數與程序，以使用沼氣作為燃料之分散式能源供應機；可避免或降低因長途輸電所損失大約10%的電力，提高熱能及電能利用效率；且本發明之沼氣觸媒熱電共生機是一種不限於使用沼氣，而是具有多功能的彈性燃料之熱電共生機。 Compared with the prior art, the present invention provides the following advantages: using biogas generated from anaerobic fermentation of food waste or excreta as fuel, which is a technology with the effect of reducing carbon emissions; simplifying the vehicle fuel catalyst disclosed in US 9,440,851 The hydrogen production catalyst reforming reactor is redesigned as a two-stage reformer and a desulfurization adsorber is added, and its operating parameters and procedures are adjusted to use biogas as a decentralized energy supply machine for fuel; it can avoid or reduce the The long-distance power transmission loses about 10% of the power, which improves the efficiency of heat and power utilization; and the biogas catalyst cogeneration machine of the present invention is a cogeneration machine that is not limited to the use of biogas, but has a multifunctional flexible fuel.

1‧‧‧風能/太陽能發電系統 1‧‧‧wind energy / solar power system

100‧‧‧PLC/ECU 100‧‧‧PLC / ECU

2‧‧‧電網 2‧‧‧ Power Grid

3‧‧‧可編程序控制器/儲電池 3‧‧‧ Programmable controller / battery

4‧‧‧氫氣儲存槽 4‧‧‧Hydrogen storage tank

5‧‧‧電解槽 5‧‧‧ electrolytic cell

6‧‧‧啟動IC引擎及發電機 6‧‧‧Start IC engine and generator

7‧‧‧氧氣儲存槽 7‧‧‧ oxygen storage tank

8‧‧‧乾燥及吸附劑槽 8‧‧‧ drying and adsorbent tank

9‧‧‧觸媒重整反應器 9‧‧‧ catalyst reforming reactor

10‧‧‧沼氣儲存槽 10‧‧‧Biogas storage tank

11‧‧‧熱交換器 11‧‧‧ heat exchanger

12‧‧‧儲水槽 12‧‧‧ water tank

13‧‧‧熱水槽 13‧‧‧ hot water tank

14‧‧‧重整氣儲存槽 14‧‧‧ reformed gas storage tank

15‧‧‧內燃機/渦輪機 15‧‧‧ Internal combustion engine / turbine

16‧‧‧發電機 16‧‧‧ Generator

17‧‧‧熱交換器 17‧‧‧Heat exchanger

20‧‧‧第一階段 20‧‧‧Phase 1

21‧‧‧第二階段 21‧‧‧Phase 2

22‧‧‧第三階段 22‧‧‧third stage

30‧‧‧控制電腦 30‧‧‧Control computer

31‧‧‧中央處理器(D2-260 CPU) 31‧‧‧Central Processing Unit (D2-260 CPU)

32‧‧‧數位輸入 32‧‧‧Digital input

33‧‧‧數位輸出 33‧‧‧Digital output

34‧‧‧熱電偶輸入 34‧‧‧Thermocouple input

35‧‧‧乙太網路 35‧‧‧ Ethernet

36‧‧‧模擬輸入 36‧‧‧ Analog Input

37‧‧‧模擬輸出 37‧‧‧Analog output

圖1為沼氣觸媒熱電共生機的流程圖。 Figure 1 is a flowchart of a biogas catalyst cogeneration unit.

圖2為兩階段觸媒部分氧化觸媒重整反應器及硫化氫吸附器的流程圖。 FIG. 2 is a flowchart of a two-stage catalyst partial oxidation catalyst reforming reactor and a hydrogen sulfide adsorber.

圖3為流量控制曲線圖，表示重整氣產量(%)和儲存容器內 重整氣壓力(atm)的函數關係。 Figure 3 is a flow control curve chart showing the reformed gas production (%) and the storage container Reforming gas pressure (atm) as a function.

圖4(a)和(b)為自動控制的硬體系統，包括一台個人電腦和一部可程式邏輯控制器。 Figure 4 (a) and (b) are hardware systems for automatic control, including a personal computer and a programmable logic controller.

本發明之一主要目的在於提供一種其包含：一沼氣儲存槽；一觸媒重整反應器，其包含顆粒狀受載型或非受載型鉑族金屬觸媒，且與該沼氣儲存槽相連接；一重整氣儲存槽，與該觸媒重整反應器相連接；及一自動控制系統，其包含控制電腦和/或微處理器、流量計/控制器、閥門、泵、傳感器、溫度計、操作的控制軟體，使沼氣儲存槽及該氧氣儲存槽提供在該觸媒重整反應器入口處的氧氣、水和沼氣之燃料混合氣，並保持O2/CH4比例在0.8以下，且(H2O+CO2)/CH4比例在10.0以下。 One of the main objects of the present invention is to provide a biogas storage tank and a catalyst reforming reactor, which includes a particulate supported or unsupported platinum group metal catalyst, and is similar to the biogas storage tank. Connection; a reformed gas storage tank connected to the catalyst reforming reactor; and an automatic control system including a control computer and / or microprocessor, flow meter / controller, valve, pump, sensor, thermometer The operating control software enables the biogas storage tank and the oxygen storage tank to provide a fuel gas mixture of oxygen, water and biogas at the entrance of the catalyst reforming reactor, and keeps the O 2 / CH 4 ratio below 0.8, and The (H 2 O + CO 2 ) / CH 4 ratio is 10.0 or less.

本文所稱之沼氣儲存槽，係包含能儲存沼氣或任何可揮發的碳氫化合物及生質能源。 The biogas storage tank referred to in this article contains the energy that can store biogas or any volatile hydrocarbons and biomass.

本文中所稱之觸媒重整反應器，包含但不限於「觸媒部分氧化(Catalytic partial oxidation，CPO)重整反應器」、「蒸氣重整反應器(Steam reformer，SR)」及「自熱重整反應器(Autothermal reformer，ATR)」係指三種不同之燃料產氫反應觸媒重整反應器，目的在於將沼氣轉化成可燃燒的H2和CO重整氣。以下為三種反應器之化學反應 The catalyst reforming reactor referred to herein includes, but is not limited to, "Catalytic partial oxidation (CPO) reforming reactor", "Steam reformer (SR)" and "Self-reforming reactor""Automatic reformer (ATR)" refers to three different fuel hydrogen production catalyst reforming reactors, the purpose of which is to convert biogas into combustible H 2 and CO reforming gas. The following are the chemical reactions of the three reactors

(1).蒸氣重整反應器(SR，吸熱反應)：CH4+H2O → CO+3 H2+206KJ/MOL (1). Steam reforming reactor (SR, endothermic reaction): CH 4 + H 2 O → CO + 3 H 2 + 206KJ / MOL

(2).觸媒部分氧化重整反應器(CPO，放熱反應)：CH4+1/2 O2 → CO+2 H2-36KJ/MOL (2). Catalyst partial oxidation reforming reactor (CPO, exothermic reaction): CH 4 +1/2 O 2 → CO + 2 H 2 -36KJ / MOL

(3).自熱重整反應器(ATR，絕熱反應)：CPO+SR 0KJ/MOL 2 CH4+1/2 O2+H2O → 2 CO+5 H2。 (3). Autothermal reforming reactor (ATR, adiabatic reaction): CPO + SR 0KJ / MOL 2 CH 4 +1/2 O 2 + H 2 O → 2 CO + 5 H 2 .

上述三種觸媒重整反應器中的任何一種皆具有相同功效，但為了降低觸媒重整反應器的體積，本發明優先選擇使用快速的觸媒部分氧化重整反應器(空間速度>100,000/hr)，而非使用包含快速觸媒部分氧化反應及較慢速之蒸氣重整反應(空間速度在2,000-8,000/hr之間)的自熱重整反應器，或是只使用慢速的蒸氣觸媒重整反應器。另外，本發明優選是採用讓內燃機或渦輪機在穩定的靜態操作模式下進行發電。因此，在觸媒重整反應器內的化學反應，其大部分的時間是在穩定靜態(stationary)狀況下進行，而沒有急速的動(瞬)態變化。即在觸媒重整反應器入口處的燃料混合氣比例、流量及反應爐的溫度都不會有急速性的瞬態變化。但若在特殊的情況下，因使用相同的控制軟體和硬體設備，本沼氣觸媒重整反應器也可以採用像車載觸媒產氫重整反應器所使用較複雜的動態操作模式。 Any of the above three catalyst reforming reactors have the same effect, but in order to reduce the volume of the catalyst reforming reactor, the present invention preferentially chooses to use a fast catalyst partial oxidation reforming reactor (space speed> 100,000 / hr) instead of using an autothermal reforming reactor containing a fast catalyst partial oxidation reaction and a slower steam reforming reaction (space velocity between 2,000-8,000 / hr), or using only slow steam Catalyst reforming reactor. In addition, the present invention preferably uses an internal combustion engine or a turbine to generate power in a stable static operation mode. Therefore, most of the chemical reaction in the catalytic reforming reactor is performed in a stable static state without rapid dynamic (transient) state changes. In other words, the proportion of fuel mixture at the inlet of the catalyst reforming reactor, the flow rate, and the temperature of the reactor will not have rapid transient changes. However, under special circumstances, because the same control software and hardware equipment are used, this biogas catalyst reforming reactor can also use more complex dynamic operation modes like the vehicle-mounted catalyst hydrogen production reforming reactor.

然而，一般而言，包含蒸氣重整反應在內的自熱重整反應器，是可以提高(H2+CO)的濃度。因此，相較於觸媒部分氧化重整反應器，操作較複雜的自熱重整反應器可以利用類似的整體鉑族金屬觸媒，來產生較多的(H2+CO)而能提高其熱效率。也就是說，若在觸媒重整反應器入口處的燃料混合氣中，加入水或水蒸氣，並在觸媒重整反應器內加入蒸氣重整觸媒劑，在不同的操作條件下，則可將觸媒部分氧化重整反應器變成自熱重整反應器，也可以將沼氣轉化成含有較多H2和CO的可燃重整氣。因此，本發明也包括使用自熱重整反應器的熱電共生機在內。 However, in general, an autothermal reforming reactor including a steam reforming reaction can increase the concentration of (H 2 + CO). Therefore, compared with the catalyst partial oxidation reforming reactor, the autothermal reforming reactor with more complicated operation can use a similar overall platinum group metal catalyst to generate more (H 2 + CO) and improve its performance. Thermal efficiency. That is, if water or water vapor is added to the fuel mixture at the entrance of the catalyst reforming reactor, and a steam reforming catalyst is added to the catalyst reforming reactor, under different operating conditions, The catalyst partial oxidation reforming reactor can be turned into an autothermal reforming reactor, and the biogas can also be converted into a combustible reforming gas containing more H 2 and CO. Therefore, the present invention also includes a thermoelectric symbiotic machine using an autothermal reforming reactor.

本文中所稱之「受載型或非受載型的鉑族金屬(supported or unsupported Pt metal group)觸媒」係指部分氧化反應中所使用之觸媒，其包含一種或多種諸如鉑(Pt)、鈀(Pd)、銠(Rh)、銥(Ir)、鋨(Os)及釕(Ru)等鉑族金屬，其為含有總鉑族金屬在0.10至2000g/ft3之間的顆粒狀受載型或非受載型鉑族金屬整體觸媒劑，如0.10、0.50、1.0、5.0、10、20、30、50、100、150、200、300、500、1000、2000g/ft3。此處所用受載型觸媒是使用整體或顆粒狀的鉑族部分觸媒，但若在不必考慮觸媒重整反應器體積大小的情況下，可在觸媒重整反應器內加入鎳(Ni)、釕(Ru)或鉑族金屬等蒸氣重整觸媒劑，並在入口混合氣內加入水或水蒸氣，而將觸媒部分氧化重整反應器(CPO)變成自熱重整反應器(ATR)。 The term "supported or unsupported Pt metal group catalyst" as used herein refers to the catalyst used in the partial oxidation reaction, which contains one or more catalysts such as platinum (Pt ), Palladium (Pd), rhodium (Rh), iridium (Ir), osmium (Os), ruthenium (Ru) and other platinum group metals, which are particulate particles containing a total platinum group metal between 0.10 and 2000 g / ft 3 Supported or unsupported platinum group metal overall catalysts, such as 0.10, 0.50, 1.0, 5.0, 10, 20, 30, 50, 100, 150, 200, 300, 500, 1000, 2000g / ft 3 . The supported catalyst used here is a whole or granular platinum group partial catalyst, but if the volume of the catalyst reforming reactor does not need to be considered, nickel (( Ni), ruthenium (Ru) or platinum group metals and other steam reforming catalysts, and water or water vapor is added to the inlet mixture to change the catalyst partial oxidation reforming reactor (CPO) into an autothermal reforming reaction (ATR).

該鉑族金屬觸媒製備程序是先將有某金屬濃度的一個或多個鉑、鈀或銠溶液浸漬在含有50至600m2/g表面積，並含有熱穩定劑的γ-氧化鋁塗層粉末上，製造成包含總鉑族金屬在0.01至10.0wt%的觸媒粉。其中熱穩定劑係指可用來保持塗層粉末在高溫下的表面積，其包括鑭、鈰、鐠、錸、鈣、鉀、鋇、釔、鋯、鍶、鎂的一種或多種氧化物及其混合物。之後再將這些催化後的觸媒粉，更進一步的塗覆在惰性整體基材的表面上。然後再乾燥和煅燒成含總鉑族金屬在0.10至2000g/ft3間的整體觸媒劑。上述惰性整體基材是具有200至600每平方英寸(CPI)直通道的陶瓷整體，其他適合之催化劑載體為陶瓷或金屬整體、泡沫、板、紗布、金屬網、態混合器等。此處多孔的陶瓷整體是從一種或多種由氧化鋁(alumina)、氧化鋁-二氧化矽(alumina-silica)、氧化鋁-二氧化矽-二氧化鈦(alumina-silica-titania)、富鋁紅柱石/莫來石(mullite)、堇青石(cordierite)、氧化鋯(zirconia)、氧化鋯-尖晶石 (zirconia-spinel)、氧化鋯莫來石(zirconia-mullite)、碳化矽(silicon carbide)等組成的金屬氧化物中選出；金屬整體可以是抗熱和抗氧化的合金，如費克拉洛伊合金(Fecralloy)、康泰爾(Kanthal)、不銹鋼(stainless steel)等。 The preparation process of the platinum group metal catalyst is to first immerse one or more platinum, palladium or rhodium solutions having a certain metal concentration in a gamma-alumina coating powder containing a surface area of 50 to 600 m 2 / g and containing a heat stabilizer. The catalyst powder is manufactured to contain 0.01 to 10.0 wt% of the total platinum group metal. The thermal stabilizer refers to the surface area of the coating powder at high temperature, which includes one or more oxides of lanthanum, cerium, praseodymium, praseodymium, calcium, potassium, barium, yttrium, zirconium, strontium, and magnesium, and mixtures thereof. . Then, these catalytic catalyst powders are further coated on the surface of the inert monolithic substrate. Then dried and calcined in platinum group metal to a total content of 0.10 to 2000g / ft 3 of the overall catalytic agent. The inert monolithic substrate is a ceramic monolith with 200 to 600 straight per square inch (CPI) straight channels. Other suitable catalyst carriers are ceramic or metal monoliths, foams, plates, gauze, metal meshes, state mixers, and the like. Here, the porous ceramics are composed of one or more of alumina, alumina-silica, alumina-silica-titania, and mullite. / Mullite, cordierite, zirconia, zirconia-spinel, zirconia-mullite, silicon carbide, etc. The selected metal oxide is selected; the metal as a whole may be a heat-resistant and oxidation-resistant alloy, such as Fecralloy, Kanthal, stainless steel, and the like.

本文所稱之「重整氣儲存槽」係可為一個或多個儲存容器/歧管來儲存所產生的乾燥重整氣，並保持在1至100大氣壓之間，以便提供該重整氣給下游的內燃機或渦輪機做唯一的燃料或是稀薄燃燒的部分燃料。 The "reformed gas storage tank" referred to herein may be one or more storage containers / manifolds to store the produced dry reformed gas and maintain it between 1 and 100 atmospheres in order to provide the reformed gas to The downstream internal combustion engine or turbine is the sole fuel or a lean-burn partial fuel.

本文中所稱之「流量控制曲線」係指一條或多條利用重整氣在儲存槽內的壓力，來同時控制在觸媒重整反應器入口處每種反應氣體的流量、反應後重整氣的氣體成分和產量，及控制觸媒重整反應器的啟動或關閉等的操作程序。且可依據儲存容器內的氣壓來調節每種反應物的流量，並在指定的O2/CH4和(H2O+CO2)/CH4比例內，提供精確的入口燃料混合氣。流量控制曲線為一條或多條利用重整氣在儲存槽內的壓力，來同時控制在觸媒重整反應器入口處每種反應氣的流量、反應後重整氣的氣體成分和產量，及控制觸媒重整反應器的啟動或關閉等的操作程序。因此，在同一條流量控制曲線上的每一點，是一組事先校正好，包含每種反應氣的流量設定值，以及觸媒重整反應器操作溫度/壓力等反應條件都預先儲存在控制電腦內。在開始操作時，可先將這組設定值下載到可程式邏輯控制器(Programmable logic controller，PLC)。若每個流量控制器都依照預先的設定值，來控制反應氣的流量，則入口燃料混合氣的O2/CH4和(H2O+CO2)/CH4比例即可被固定住；當入口燃料混合氣的氣體成分被固定後，快速又完全的觸媒反應也會依照反應的溫度，來產生固定的重整氣的產量和氣體成 分。然而，若在同條控制曲線上的每點，都被設定有相同混合氣的O2/CH4和(H2O+CO2)/CH4比例時，便可以產生相同氣體成份的重整氣。但由於同一條曲線上的每點卻有不同的流量設定值。因此，控制曲線便可依照儲存槽內觸媒重整氣的壓力，來控制重整氣的產量。不同的燃料會有不同的控制曲線，也會有不同預先校正好的流量設定值。因此，同一部熱電共生機，也可以利用不同的控制曲線，成功的從不同的燃料來產生含(H2+CO)的可燃重整氣，並供給下游的內燃機或渦輪機做唯一的燃料或做稀薄燃燒的部分燃料。換句話說，若內燃機或渦輪機使用含(H2+CO)的可燃重整氣做唯一的燃料，則任何可揮發的碳氫化合物及生質能源，都可以使用相同的設備來產生含(H2+CO)的可燃重整氣，以供應熱與電的日常必需品。因此，本沼氣觸媒熱電共生機，是一部具有多功能的彈性燃料熱電共生機。 The “flow control curve” referred to in this article refers to the use of the pressure of the reforming gas in the storage tank to simultaneously control the flow of each reaction gas at the entrance of the catalyst reforming reactor and the post-reaction reforming. The gas composition and output of gas, and the operating procedures for controlling the startup or shutdown of the catalyst reforming reactor. The flow rate of each reactant can be adjusted according to the air pressure in the storage container, and accurate inlet fuel mixture can be provided within the specified O 2 / CH 4 and (H 2 O + CO 2 ) / CH 4 ratio. The flow control curve is one or more utilizing the pressure of the reformed gas in the storage tank to simultaneously control the flow of each reaction gas at the inlet of the catalyst reforming reactor, the gas composition and output of the reformed gas after the reaction, and Control the operation procedure of the catalyst reforming reactor, such as startup or shutdown. Therefore, each point on the same flow control curve is a set of corrections in advance. The reaction conditions including the flow setting value of each reaction gas and the operating temperature / pressure of the catalyst reforming reactor are stored in the control computer in advance. Inside. At the beginning of the operation, this set of settings can be downloaded to a Programmable Logic Controller (PLC). If each flow controller controls the flow rate of the reactant gas according to a preset value, the O 2 / CH 4 and (H 2 O + CO 2 ) / CH 4 ratios of the inlet fuel mixture can be fixed; When the gas composition of the inlet fuel mixture is fixed, the fast and complete catalyst reaction will also generate a fixed reformed gas production and gas composition according to the reaction temperature. However, if at each point on the same control curve, the O 2 / CH 4 and (H 2 O + CO 2 ) / CH 4 ratios of the same mixture are set, a reformation of the same gas composition can be generated gas. But each point on the same curve has a different flow setting. Therefore, the control curve can control the reformed gas production according to the pressure of the catalyst reformed gas in the storage tank. Different fuels will have different control curves and different pre-calibrated flow settings. Therefore, the same thermoelectric generator can also use different control curves to successfully generate combustible reformed gas containing (H 2 + CO) from different fuels and supply it to the downstream internal combustion engine or turbine as the sole fuel or Partially burned fuel. In other words, if the internal combustion engine or turbine uses combustible reformed gas containing (H 2 + CO) as the sole fuel, any volatile hydrocarbon and biomass energy can use the same equipment to generate (H 2 + CO) combustible reformed gas to supply daily necessities of heat and electricity. Therefore, the biogas catalyst cogeneration unit is a multifunctional flexible fuel cogeneration unit.

於一較佳實施例，其中該流量控制曲線包含：(a)在同一條控制曲線上的每個點，是一組預先校正好，可供應同一特定O2/CH4和(H2O+CO2)/CH4比例的燃料混合氣，也能輸出每點不同並預先設定好的重整氣總量但相同濃度的重整氣；(b)不同的控制曲線包括不同預先校正好的特定O2/CH4和(H2O+CO2)/CH4比例，可以輸出不同的重整氣總量和不同濃度的重整氣；(c)不同的燃料可以用不同預先校正好的控制曲線，來控制O2/C和(H2O+CO2)/C比例(其中O2/C比例中的C是燃料C，並不包含在入口燃料中的CO2在內)，並使用相同的機器及設備來產生含(H2+CO)的可燃重整氣，供做內燃機或渦輪機的燃料。 In a preferred embodiment, the flow control curve includes: (a) each point on the same control curve is a set of pre-calibrated and can supply the same specific O 2 / CH 4 and (H 2 O + CO 2 ) / CH 4 ratio fuel mixture can also output the reformed gas with different preset total amount but the same concentration of reformed gas at different points; (b) different control curves include different pre-calibrated specific O 2 / CH 4 and (H 2 O + CO 2 ) / CH 4 ratios can output different amounts of reformed gas and reformed gas with different concentrations; (c) different fuels can be controlled with different pre-calibrated controls Curve to control the O 2 / C and (H 2 O + CO 2 ) / C ratios (where C in the O 2 / C ratio is fuel C, not including CO 2 in the inlet fuel), and use The same machines and equipment are used to produce combustible reformed gas containing (H 2 + CO) for use as fuel for internal combustion engines or turbines.

一般而言，沼氣含有55-60%甲烷(CH4)、40-45%二氧化碳(CO2)、0.4-1.2%氮(N2)、0.0-0.4%氧(O2)和0.02-0.4%硫化氫(H2S)。因為沼氣 己經含有大量的CO2，且CO2有很大的熱容量。所以在理論上CO2是可以取代水或水蒸氣，來調節並控制觸媒重整反應器內的反應溫度在1200℃以下。即，在觸媒重整反應器的入口沼氣混合氣中，可以降低H2O/CH4的比例及提高CO2/CH4的比例。依據US 9,440,851揭示的車載觸媒重整反應器，為了控制觸媒重整反應器內觸媒的溫度在1200℃以下，若使用CH4做燃料，則其入口燃料混合物的H2O/CH4比例保持在0.05至10.0之間為佳，O2/CH4比例在0.15到0.8之間和CO2/CH4在0.0和0.5之間。但由於沼氣入口混合氣內含大量的CH4和CO2，所以在觸媒重整反應器的入口沼氣混合氣中，可以降低H2O/CH4的比例，並提高CO2/CH4的比例來調整觸媒劑的溫度。因此，本觸媒重整反應器的入口沼氣混合氣，其O2/CH4比例保持在0.8以下，而(H2O+CO2)/CH4比例應保持在10.0以下。一般而言，必需保持觸媒重整反應器內的反應溫度在1200℃以下，才能延長觸媒使用年限並保持觸媒對沼氣的高反應轉化率。 Generally speaking, biogas contains 55-60% methane (CH 4 ), 40-45% carbon dioxide (CO 2 ), 0.4-1.2% nitrogen (N 2 ), 0.0-0.4% oxygen (O 2 ), and 0.02-0.4% Hydrogen sulfide (H 2 S). Because biogas already contains a large amount of CO 2 , and CO 2 has a large heat capacity. Therefore, in theory, CO 2 can replace water or water vapor to adjust and control the reaction temperature in the catalyst reforming reactor below 1200 ° C. That is, in the inlet biogas mixture of the catalyst reforming reactor, the ratio of H 2 O / CH 4 and the ratio of CO 2 / CH 4 can be increased. According to the vehicle-mounted catalyst reforming reactor disclosed in US 9,440,851, in order to control the temperature of the catalyst in the catalyst reforming reactor below 1200 ° C, if CH 4 is used as the fuel, the inlet fuel mixture H 2 O / CH 4 It is better to keep the ratio between 0.05 and 10.0, with the O 2 / CH 4 ratio between 0.15 and 0.8 and CO 2 / CH 4 between 0.0 and 0.5. But because the biogas inlet mixture contains a large amount of CH 4 and CO 2 , the ratio of H 2 O / CH 4 can be reduced and the CO 2 / CH 4 ratio can be increased in the biogas mixture at the inlet of the catalytic reforming reactor. Ratio to adjust the temperature of the catalyst. Therefore, at the inlet biogas mixture of the catalyst reforming reactor, the O 2 / CH 4 ratio should be kept below 0.8, and the (H 2 O + CO 2 ) / CH 4 ratio should be kept below 10.0. Generally speaking, it is necessary to keep the reaction temperature in the catalyst reforming reactor below 1200 ° C in order to extend the useful life of the catalyst and maintain a high reaction conversion rate of the catalyst to the biogas.

依據US 4,522,894及US 9,440,851所揭示之技術特徵，若觸媒重整反應器入口燃料混合氣的O2/CH4低於0.50時，所有的O2將會全部反應，而碳氫燃料的轉化率則保持在100%以下。因此，可以利用O2/CH4的比例為0.08-0.50，以控制沼氣中CH4的轉化率，進而調整所產生重整氣中(H2+CO)/CH4的比例，而變成含H2和CH4的氫烷混合氣(Hythane)。換句話說，若控制觸媒重整反應器入口的O2/CH4比例在0.08-0.50時，所有的氧氣將被全部轉化成(H2+CO)重整氣，但所產生的重整氣仍含有未反應的CH4。因此，可以有效的利用O2/CH4比例製造含不同(H2+CO)/CH4比例的混合燃料(Hythane)，再利用易燃的氫氣和CO來幫助內燃機，做高壓縮比例的稀薄燃 燒，來提升沼氣/天然煤氣內燃機的燃燒效率，並降低其污染氣的排放量。 According to the technical characteristics disclosed in US 4,522,894 and US 9,440,851, if the O 2 / CH 4 of the fuel mixture at the inlet of the catalyst reforming reactor is lower than 0.50, all O 2 will react completely, and the conversion rate of hydrocarbon fuel It stays below 100%. Therefore, the ratio of O 2 / CH 4 can be 0.08-0.50 to control the conversion rate of CH 4 in the biogas, and then adjust the ratio of (H 2 + CO) / CH 4 in the reformed gas to become H-containing Hydane gas mixture of 2 and CH 4 (Hythane). In other words, if the O 2 / CH 4 ratio at the inlet of the catalyst reforming reactor is controlled at 0.08-0.50, all the oxygen will be completely converted into (H 2 + CO) reforming gas, but the reforming produced gas still contains unreacted CH 4. Therefore, the O 2 / CH 4 ratio can be effectively used to produce mixed fuels (Hythane) with different (H 2 + CO) / CH 4 ratios, and then flammable hydrogen and CO are used to help the internal combustion engine to make lean with high compression ratio. Combustion to improve the combustion efficiency of biogas / natural gas internal combustion engines and reduce their emissions of polluted gas.

其中該重整氣(H2+CO)作為內燃機或渦輪機之唯一的燃料時，在緊急情況下，可使用天然煤氣、液化煤氣、生質酒精、甲醇、汽油、柴油、生質柴油或其他可揮發的碳氫化合物來取代沼氣作為備用燃料，以有效率的利用該沼氣觸媒熱電共生機。 When the reformed gas (H 2 + CO) is used as the sole fuel of the internal combustion engine or turbine, in an emergency, natural gas, liquefied gas, bio-ethanol, methanol, gasoline, diesel, bio-diesel, or other Volatile hydrocarbons are used to replace biogas as a backup fuel to efficiently use the biogas catalyst cogeneration unit.

本文所稱之氧氣儲存槽，係作用為提供純氧來代替空氣，使沼氣在經過觸媒部分氧化反應或自熱重整反應後，可以提高出口重整氣的(H2+CO)濃度(%)。 The oxygen storage tank referred to herein is to provide pure oxygen instead of air, so that the biogas can increase the (H 2 + CO) concentration of the reformed gas at the outlet after the catalytic partial oxidation reaction or autothermal reforming reaction ( %).

其中，若使用沼氣或天然煤氣做燃料，並控制觸媒重整反應器入口燃料混合氣之O2/CH4比例在0.08-0.50時，可以有效的製造H2/CH4不同比例的混合氣，以取代純天然煤氣做內燃機的燃料，提升內燃機/渦輪機的燃燒效率，並降低其污染氣體的排放量。於一較佳實施例，其他內燃機/渦輪機的燃料，如：天然煤氣、液化煤氣、生質酒精、甲醇、汽油、柴油、生質柴油以及可揮發的碳氫化合物等，也可利用該沼氣觸媒熱電共生機所提供的觸媒轉化及除硫設備及其方法來去除在燃料內所含的硫化合物。 Among them, if biogas or natural gas is used as the fuel, and the O 2 / CH 4 ratio of the fuel mixture at the inlet of the catalyst reforming reactor is 0.08-0.50, it is possible to effectively produce mixtures with different H 2 / CH 4 ratios. To replace pure natural gas as fuel for internal combustion engines, improve the combustion efficiency of internal combustion engines / turbines and reduce their emissions of pollutant gases. In a preferred embodiment, other internal combustion engine / turbine fuels, such as: natural gas, liquefied gas, bio-ethanol, methanol, gasoline, diesel, bio-diesel, and volatile hydrocarbons, etc. Catalyst conversion and desulfurization equipment and methods provided by the diastereoelectric symbiotic machine to remove sulfur compounds contained in the fuel.

於一較佳實施例，其中該預先設定的控制曲線可以利用該儲存容器內的重整氣壓力，來調節每種反應物的流量，並因此來增加或減少由CPO/ATR觸媒重整反應器所產生重整氣的總量。 In a preferred embodiment, the preset control curve can use the reforming gas pressure in the storage container to adjust the flow rate of each reactant, and thus increase or decrease the reforming reaction by the CPO / ATR catalyst. The total amount of reformed gas produced by the reactor.

本發明另一主要目的在於提供一種如本發明之沼氣觸媒熱電共生機之方法，其包含：提供一條或多條儲存在該控制電腦和/或該微處理器內的流量控制曲線，並依據各儲存槽內的氣壓來調節流量，使沼氣儲存槽及該氧氣儲存槽提供在該觸媒重整反應器入口處的氧氣、水和沼氣之 燃料混合氣，保持O2/CH4比例在0.8以下，且(H2O+CO2)/CH4比例在10.0以下。 Another main object of the present invention is to provide a biogas catalyst cogeneration machine method according to the present invention, which includes: providing one or more flow control curves stored in the control computer and / or the microprocessor, and based on The air pressure in each storage tank is used to adjust the flow rate, so that the biogas storage tank and the oxygen storage tank provide a fuel gas mixture of oxygen, water and biogas at the entrance of the catalyst reforming reactor, keeping the O 2 / CH 4 ratio at 0.8 The ratio of (H 2 O + CO 2 ) / CH 4 is 10.0 or less.

其中，本發明之方法包含觸媒重整反應器之三階段反應，第一階段為觸媒部分氧化重整反應器，控制O2/CH4在0.08到0.25之間，反應器溫度在200℃到500℃之間，且在含0-5%(H2+水蒸氣)的情況下，將沼氣內所有的硫化合物在經過顆粒狀受載型或非受載型鉑族金屬觸媒時，全部轉化成硫化氫；第二階段，利用一種或多種，如：鋅、鎳、銅、鈷、沸石、鐵、鋁或銅/鋅等氧化物或混合氧化物做為硫化氫的吸附劑，並在200-500℃之間脫硫；第三階段，利用第二階段的觸媒部分氧化重整反應器或自燃觸媒重整反應器，再加入更多的氧氣以提高O2/CH4比例，並提高沼氣中甲烷的反應轉換率和出口重整氣的產量。 Among them, the method of the present invention includes a three-stage reaction of a catalyst reforming reactor. The first stage is a catalyst partial oxidation reforming reactor, which controls O 2 / CH 4 between 0.08 and 0.25, and the reactor temperature is 200 ° C. When the temperature is between 500 ° C and 0-5% (H 2 + water vapor), all sulfur compounds in the biogas are passed through a particulate supported or unsupported platinum group metal catalyst. All are converted into hydrogen sulfide; in the second stage, one or more oxides or mixed oxides such as zinc, nickel, copper, cobalt, zeolite, iron, aluminum or copper / zinc are used as adsorbents for hydrogen sulfide, and Desulfurization between 200-500 ℃; in the third stage, the catalyst in the second stage is used to partially oxidize the reforming reactor or the self-igniting catalyst reforming reactor, and then add more oxygen to increase the O 2 / CH 4 ratio , And increase the conversion rate of methane in biogas and the output of reformed gas at the outlet.

於一較佳實施例，其中第一階段只含0-5%(H2+水蒸氣)，其是利用降低水蒸氣的含量來增加下游ZnO、銅/鋅等氧化物吸附劑的H2S吸附總量，以及利用氫和氧的反應熱來增加觸媒的溫度，並增加硫化合物和甲烷的觸媒部分氧化反應速度。 In a preferred embodiment, the first stage contains only 0-5% (H 2 + water vapor), which is to reduce the content of water vapor to increase the H 2 S of downstream oxide adsorbents such as ZnO, copper / zinc, etc. The total amount of adsorption, and the use of the heat of reaction of hydrogen and oxygen to increase the temperature of the catalyst, and to increase the speed of the partial oxidation reaction of the catalyst of sulfur compounds and methane.

依據本發明，由厭氧醱酵槽所產生的沼氣，儲存於沼氣儲存槽中，並可以先用乾燥或吸附劑來移除水份及雜質。乾燥後的沼氣可直接做內燃機或渦輪機的燃料，並帶動發電機來供應電力給自動控制系統的電腦及儀器。同時，也可以利用風能、太陽能、電網或預先儲存在電瓶內的電源來操作此控制系統，及利用剩餘的電力來電解水而產生純氧氣及純氫氣。若在正常的操作情況下，所產生的氫氣可應用在內燃機做稀薄燃燒時所需的部份燃料，來提高其熱效率；而氧氣則可以代替空氣做沼氣的觸媒部分氧化反應，來產生含H2和CO的重整氣。若使用純氧和純甲烷的混合 氣，此觸媒重整反應器因不含使用空氣時所帶進來的氮氣，觸媒部分氧化反應是可以將(H2+CO)的濃度從約40%提高到60%左右。但若使用自熱重整反應，其濃度則可由大約53%提高到73%。如果所產生的重整氣在經過冷卻及壓縮後，便可以被儲存在高壓的儲存槽內，供應做下游內燃機或渦輪機的燃料，並帶動發電機來發電。最後，內燃機或渦輪機的廢氣也可以經過熱交換器來提供熱氣及熱水，供作日常生活的必需品。 According to the present invention, the biogas produced by the anaerobic fermentation tank is stored in the biogas storage tank, and moisture or impurities can be removed by using a drying or adsorbent. The dried biogas can be directly used as fuel for internal combustion engines or turbines, and drive generators to supply electricity to computers and instruments of automatic control systems. At the same time, the control system can also be operated using wind energy, solar energy, the power grid or a power source stored in a battery in advance, and the remaining electricity can be used to electrolyze water to produce pure oxygen and pure hydrogen. Under normal operating conditions, the hydrogen produced can be used as part of the fuel required for lean combustion in internal combustion engines to improve its thermal efficiency; and oxygen can replace air as a catalyst for partial oxidation of biogas to produce the H 2 and CO reformed gas. If a mixture of pure oxygen and pure methane is used, the catalyst reforming reactor does not contain nitrogen brought in when using air, and the partial oxidation reaction of the catalyst can reduce the concentration of (H 2 + CO) from about 40% Raise to about 60%. However, if an autothermal reforming reaction is used, the concentration can be increased from about 53% to 73%. If the generated reformed gas is cooled and compressed, it can be stored in a high-pressure storage tank, supplied as fuel for downstream internal combustion engines or turbines, and driven by a generator to generate electricity. Finally, exhaust gases from internal combustion engines or turbines can also pass through heat exchangers to provide hot air and hot water for daily necessities.

依據美國專利US 9,440,851所揭示，任何可揮發的碳氫化合物例如天然煤氣、液化煤氣、生質酒精、甲醇、汽油、柴油、生質柴油以及可揮發的碳氫化合物等，都可以被這些整體鉑族金屬觸媒，在適當的反應條件下轉化成含有H2和CO的重整氣，給下游的內燃機/渦輪機15做唯一的燃料。因此，在緊急或在特殊必要的情況下，任何可揮發的碳氫化合物及生質能源，若選擇合適的控制曲線，都可以利用相同的設備，而成為本發明沼氣觸媒熱電共生機的燃料，即該熱電共生機是一部具有多功能及彈性燃料的熱電共生機。 According to U.S. Patent No. 9,440,851, any volatile hydrocarbons such as natural gas, liquefied gas, bio-ethanol, methanol, gasoline, diesel, bio-diesel, and volatile hydrocarbons, etc., can be covered by these overall platinum. The group metal catalyst is converted into a reformed gas containing H 2 and CO under appropriate reaction conditions, and is used as the sole fuel for the internal combustion engine / turbine 15 downstream. Therefore, in an emergency or under special necessary conditions, if any volatile hydrocarbon and biomass energy are selected, if the appropriate control curve is selected, the same equipment can be used to form the fuel of the biogas catalyst cogeneration machine of the present invention. That is, the thermoelectric symbiotic machine is a thermoelectric symbiotic machine with multifunctional and flexible fuel.

其他內燃機/渦輪機的燃料，像天然煤氣、液化煤氣、生質酒精、甲醇、汽油、柴油、生質柴油以及可揮發的碳氫化合物等，可作為備用或緊急燃料，也可以利用本沼氣觸媒熱電共生機，所提供的觸媒轉化及除硫的設備和操作這些裝置的方法來脫(除)硫。也就是說，若在第一階段先控制O2/C在0.08-0.25之間(即O2/C比例中的C是燃料C，並不包含在入口燃料中的CO2在內)，及含0-5%(H2+水蒸氣)的情況下來產氫和硫化氫。則這裡所提出的觸媒部分氧化重整反應器、硫化氫吸附器和部分氧化觸媒重整反應器或自燃觸媒重整反應器的兩種組合，可以有效的除去在上述任何燃料 中所含有的碳氫硫化合物。 Other internal combustion engine / turbine fuels, such as natural gas, liquefied gas, bio-alcohol, methanol, gasoline, diesel, bio-diesel, and volatile hydrocarbons, etc., can be used as backup or emergency fuels, or you can use this biogas catalyst Thermoelectric symbiotic machine, provided catalyst conversion and desulfurization equipment and methods for operating these devices to desulfurize (desulfurize). That is, if the O 2 / C is controlled between 0.08-0.25 in the first stage (that is, C in the O 2 / C ratio is fuel C, and CO 2 is not included in the inlet fuel), and With 0-5% (H 2 + water vapor), hydrogen and hydrogen sulfide are produced. Then the two combinations of catalyst partial oxidation reforming reactor, hydrogen sulfide adsorber and partial oxidation reforming reactor or self-ignition catalyst reforming reactor proposed here can effectively remove all of the above-mentioned fuels. Contained hydrocarbon sulfur compounds.

於此，本發明將以下方實施例進一步說明，然而，需理解於此之實施例並非用以限定本發明之範圍。 Herein, the present invention further illustrates the following embodiments, however, it should be understood that the embodiments herein are not intended to limit the scope of the present invention.

[實施例][Example]

圖1為沼氣觸媒熱電共生機的流程圖。首先，經厭氧醱酵槽所產生的沼氣，可儲存在圖1中之沼氣儲存槽10內。在使用時此沼氣可先經過乾燥及吸附劑槽8，將所含的水分及部分硫化氫去除。目前在市面上較普遍使用的沼氣脫硫化氫的技術是水洗、鹼水洗(如：氫氧化鉀、氫氧化鈉、氫氧化鈣、乙醇胺等)、吸附劑(如：氧化鐵或活性碳等)、變壓分離或生物脫硫等方式。由乾燥及吸附劑槽8出來的乾燥沼氣可直接做啟動IC引擎及發電機6的燃料來發電，並供應電力給電腦及控制儀器來自動操作整個沼氣觸媒熱電共生機。若有剩餘的電力，可和提供電力於可編程序控制器/儲電池3之風能/太陽能發電系統1或電網2的電力，在電解槽5內將水電解產生純氧氣及純氫氣。該氧氣及氫氣可被各自儲存在氧氣儲存槽7及氫氣儲存槽4；氫氣儲存槽4內的純氫氣可用來協助並提升啟動IC引擎及發電機6的燃燒效率；而氧氣儲存槽7內的純氧氣可代替空氣來做觸媒重整反應器9內的觸媒部分氧化反應，來提高所產生重整氣的H2和CO濃度。 Figure 1 is a flowchart of a biogas catalyst cogeneration unit. First, the biogas produced by the anaerobic fermentation tank can be stored in the biogas storage tank 10 shown in FIG. 1. In use, this biogas can first pass through the drying and adsorbent tank 8 to remove the water and part of the hydrogen sulfide. At present, the more commonly used biogas dehydrosulfide technology in the market is water washing, alkaline washing (such as: potassium hydroxide, sodium hydroxide, calcium hydroxide, ethanolamine, etc.), adsorbents (such as: iron oxide or activated carbon, etc.) , Pressure swing separation or biological desulfurization. The dry biogas from the drying and adsorbent tank 8 can be directly used as fuel for starting the IC engine and generator 6 to generate electricity, and supply power to computers and control instruments to automatically operate the entire biogas catalyst cogeneration machine. If there is surplus power, the electricity can be supplied to the wind power / solar power generation system 1 or grid 2 of the programmable controller / storage battery 3 to electrolyze water in the electrolytic cell 5 to produce pure oxygen and pure hydrogen. The oxygen and hydrogen can be stored in the oxygen storage tank 7 and the hydrogen storage tank 4 respectively; the pure hydrogen in the hydrogen storage tank 4 can be used to assist and improve the combustion efficiency of starting the IC engine and the generator 6; and the oxygen storage tank 7 Pure oxygen can be used instead of air for the catalyst partial oxidation reaction in the catalyst reforming reactor 9 to increase the H 2 and CO concentrations of the reformed gas produced.

當觸媒重整反應器9開始時，沼氣和氧的入口混合氣必需在最低反應溫度以上(約250-320℃左右)，部分氧化反應才會快速的發生。因此，觸媒重整反應器9可以使用下列的任何一個方式來預熱：(1)利用啟動IC引擎及發電機6的廢氣；(2)利用氫氣儲存槽4和氧氣儲存槽7內的氫氣及氧氣，在經過整體鉑族觸媒時所產生的反應熱；及(3)利用點燃沼氣和氧氣的 混合氣來產生燃燒熱。因為氫氣和氧氣在室溫時，便可利用鉑族觸媒來反應而產生氧化熱，是很有效的預熱方式。但當部分氧化反應開始發生後，自己產生的氧化熱，便能持續的保持觸媒劑在最低反應溫度以上。 When the catalytic reforming reactor 9 is started, the inlet gas mixture of biogas and oxygen must be above the minimum reaction temperature (about 250-320 ° C), so that the partial oxidation reaction will occur quickly. Therefore, the catalyst reforming reactor 9 can be preheated in any of the following ways: (1) using exhaust gas from the start-up IC engine and generator 6; (2) using hydrogen in the hydrogen storage tank 4 and the oxygen storage tank 7 And oxygen, the reaction heat generated when passing through the whole platinum group catalyst; and (3) the use of ignited biogas and oxygen Mix gas to generate heat of combustion. Because hydrogen and oxygen can react with platinum group catalysts to generate oxidation heat at room temperature, it is a very effective preheating method. However, after the partial oxidation reaction begins, the oxidation heat generated by itself can keep the catalyst above the minimum reaction temperature.

圖2所示為三階段觸媒部分氧化重整反應器及氧化物吸附劑的流程圖。首先，在第一階段20觸媒部分氧化重整反應器的入口先噴入沼氣、純氧或空氣及少量的0%-5%(H2+H2O)氣體，使整個混合氣的O2/CH4比例調整在0.08到0.25之間，並控制第一階段反應器的溫度在200到500℃之間。在此情況下，所有的硫化合物可以被轉化成硫化氫。所加入0%-5%(H2+H2O)的氣體可以在需要時用氫和氧的反應熱，來增加觸媒劑的溫度，並加速硫化合物和甲烷的部分氧化反應。然後，第二階段21為在第一階段出口重整氣中的硫化氫，可被一種或多種諸如鋅、鎳、銅、鈷、沸石、鐵、鋁或銅/鋅等氧化物或混合氧化物吸附劑吸收而除硫。接著第三階段22，可在觸媒部分氧化重整反應器前，再噴入更多的氧氣，以將所有在沼氣中的甲烷轉化成含H2和CO的出口燃料重整氣。如果需要，此出口重整氣在冷卻後，剩餘的硫化氫可再經過氧化吸附劑來完全除硫。泠卻後的出口可燃重整氣，可以直接做內燃機或氣渦輪機的燃料，或是加入更多的除硫沼氣及空氣而變成稀薄燃燒的混合氣。 FIG. 2 shows a flow chart of a three-stage catalyst partial oxidation reforming reactor and an oxide adsorbent. First, in the first stage, the inlet of the 20-catalyst partial oxidation reforming reactor is first injected with biogas, pure oxygen or air and a small amount of 0% -5% (H 2 + H 2 O) gas, so that the O of the entire mixed gas The 2 / CH 4 ratio is adjusted between 0.08 and 0.25, and the temperature of the first stage reactor is controlled between 200 and 500 ° C. In this case, all sulfur compounds can be converted into hydrogen sulfide. The added 0% -5% (H 2 + H 2 O) gas can use the reaction heat of hydrogen and oxygen when necessary to increase the temperature of the catalyst and accelerate the partial oxidation reaction of sulfur compounds and methane. Then, the second stage 21 is the hydrogen sulfide in the reformed gas at the outlet of the first stage, and may be one or more oxides or mixed oxides such as zinc, nickel, copper, cobalt, zeolite, iron, aluminum, or copper / zinc. The adsorbent absorbs and removes sulfur. Following the third stage 22, before the catalyst is partially oxidized to the reforming reactor, more oxygen can be injected to convert all the methane in the biogas into an outlet fuel reforming gas containing H 2 and CO. If required, after the outlet reformed gas is cooled, the remaining hydrogen sulfide can be passed through an oxidizing adsorbent to completely remove sulfur. The combustible reformed gas at the exit of the cooling can be directly used as fuel for internal combustion engines or gas turbines, or it can be added into a lean-burning mixed gas by adding more desulfurization biogas and air.

如前所述，上述脫硫的第二階段觸媒重整反應器21也可以加入適當比例的純氧/空氣和水/水蒸氣來取代部分氧化反應，而變成做自熱重整反應來從沼氣中產生重整氣。也就是說，圖2也可以是部分氧化重整反應器、硫化氫吸附器和觸媒部分氧化重整反應器或自熱重整反應器的組合。事實上，其他內燃機/渦輪機的燃料，如：天然煤氣、液化煤氣、生質酒精、 甲醇、汽油、柴油、生質柴油以及可揮發的碳氫化合物等，也可以利用本觸媒轉化及除硫設備和操作程序來完全脫(除)硫。 As mentioned above, the above-mentioned second stage catalytic reforming reactor 21 for desulfurization can also add appropriate proportions of pure oxygen / air and water / water vapor to replace the partial oxidation reaction, and instead become an autothermal reforming reaction to Reformed gas is produced in the biogas. That is, FIG. 2 may also be a combination of a partial oxidation reforming reactor, a hydrogen sulfide adsorber, and a catalyst partial oxidation reforming reactor or an autothermal reforming reactor. In fact, other internal combustion engine / turbine fuels, such as: natural gas, liquefied gas, bio-alcohol, Methanol, gasoline, diesel, biodiesel, and volatile hydrocarbons can also be completely desulfurized (desulfurized) using this catalyst conversion and desulfurization equipment and operating procedures.

根據圖1及圖2所述，沼氣的部分氧化反應可分成兩個階段在觸媒重整反應器9內進行，便能將全部的硫化氫吸附來除硫，也能將部分或全部的沼氣轉化成H2和CO重整氣。除硫後，從觸媒重整反應器9出來的重整氣，可在連接有熱水槽13及儲水槽12之熱交換器11內經泠卻後而被存入重整氣儲存槽14內，並做內燃機/渦輪機15的燃料來帶動發電機16發電。最後，內燃機/渦輪機15的廢氣可經過熱交換器17來產生熱水和熱氣，供做日常生活的必需品。 According to FIG. 1 and FIG. 2, the partial oxidation reaction of biogas can be divided into two stages and carried out in the catalyst reforming reactor 9, so that all the hydrogen sulfide can be adsorbed to remove sulfur, and some or all of the biogas can be also removed. Conversion to H 2 and CO reformed gas. After desulfurization, the reformed gas from the catalyst reforming reactor 9 can be stored in the reformed gas storage tank 14 after being cooled in the heat exchanger 11 connected to the hot water tank 13 and the water storage tank 12, The fuel of the internal combustion engine / turbine 15 is used to drive the generator 16 to generate electricity. Finally, the exhaust gas from the internal combustion engine / turbine 15 can pass through the heat exchanger 17 to generate hot water and hot gas for daily necessities.

圖3所示為預先校正好的控制曲線，其中重整氣產量(%)為從CPO或ATR輸出的重整氣總量，作為儲存槽內重整氣壓力的函數。在曲線上的每個點是包括一組預先校正好，有關於所有流量計/控制器的設定值的完整組合。因此，每個點可供應同一特定O2/CH4，(H2O+CO2)/CH4比例的燃料混合氣，也同時能產生並輸出預先設定的重整氣總量。在通常的情況下，每個完整組的設定點是從PC下載到PLC，PLC再將這組預先校正好的設定值，發送到在系統中每個流量計/控制器，並相對地調整每個反應物的流量。若將所有的單一反應物混合在一起，觸媒重整反應器入口燃料混合氣的O2/CH4和(H2O+CO2)/CH4比例可以被控制在一個特定值，因此，觸媒重整反應器可以產生相同組成的重整氣。換言之，在此一控制曲線上的每一個點，都可以實際提供相同組成的燃料混合氣，並可產生相同組成的重整氣，但有不同的總流量。同樣地，不同預先校正好的控制曲線，也可以提供不同O2/CH4和(H2O+CO2)/CH4比例的燃料混合氣，和供應各種不同流量和 組合的重整氣。 Figure 3 shows a pre-corrected control curve, in which the reformed gas output (%) is the total reformed gas output from the CPO or ATR as a function of the reformed gas pressure in the storage tank. Each point on the curve includes a set of pre-calibrated, complete sets of settings for all flow meters / controllers. Therefore, each point can supply the same specific O 2 / CH 4 , (H 2 O + CO 2 ) / CH 4 ratio fuel mixture, and can also generate and output a preset total amount of reformed gas. Under normal circumstances, the setpoints of each complete group are downloaded from the PC to the PLC, and the PLC sends this set of pre-calibrated settings to each flowmeter / controller in the system and adjusts each The flow rate of each reactant. If all the single reactants are mixed together, the O 2 / CH 4 and (H 2 O + CO 2 ) / CH 4 ratio of the fuel mixture at the inlet of the catalyst reforming reactor can be controlled to a specific value. Therefore, Catalyst reforming reactors can produce reforming gases of the same composition. In other words, at each point on this control curve, a fuel mixture of the same composition can be actually provided and a reformed gas of the same composition can be produced, but with different total flows. Similarly, different pre-calibrated control curves can also provide fuel mixtures with different O 2 / CH 4 and (H 2 O + CO 2 ) / CH 4 ratios, and supply reforming gases with various flows and combinations.

圖4所示為自動控制系統，其細部設施如圖4(b)所示。其中包含一組可程式邏輯控制器(PLC)/排放控制單元(ECU)100、中央處理器(DL-260)31、數位輸入32、數位輸出33、模擬輸入36、模擬輸出37、乙太網路35以及熱電偶輸入34的模組硬體設備，並由電腦30所控制。該控制系統設備簡單且成本低，其中閥門連接到數位輸出33膜組；進一步包含質量流量計(Tylan質量流量計)(圖中未示)和水計量泵(圖中未示)連接到模擬輸出36及模擬輸入37模組；K型熱電偶則連接到熱電偶輸入34模組。 Figure 4 shows the automatic control system, and its detailed facilities are shown in Figure 4 (b). It contains a set of programmable logic controller (PLC) / emission control unit (ECU) 100, central processing unit (DL-260) 31, digital input 32, digital output 33, analog input 36, analog output 37, Ethernet The module hardware equipment of circuit 35 and thermocouple input 34 is controlled by computer 30. The control system is simple and low-cost. The valve is connected to the digital output 33 membrane group. It further includes a mass flow meter (Tylan mass flow meter) (not shown) and a water metering pump (not shown) connected to the analog output. 36 and analog input 37 modules; K type thermocouple is connected to thermocouple input 34 module.

主控制電腦為一台使用Windows XP的宏基Aspire One小筆記型電腦。利用Visual Basic書寫的主控制軟件，是用來下載流量控制器的設定點、開/關閥門、監測/控制反應器溫度、監視/記錄每個設備操作狀況、自動操作產氫反應器，並執行實驗程序。對於一個較小的系統，圖4所述電腦30和PLC/ECU 100的功能可以被一個功能強大的微處理器或被一個安裝了必要I/O模組小型PC所取代。因此，該自動操作系統可以很容易地由一個功能強大的替代控制裝置來完成。 The main control computer is an Acer Aspire One small notebook computer using Windows XP. The main control software written in Visual Basic is used to download the set points of the flow controller, open / close the valve, monitor / control the reactor temperature, monitor / record the operating status of each device, automatically operate the hydrogen production reactor, and execute Experimental procedures. For a smaller system, the functions of the computer 30 and PLC / ECU 100 described in FIG. 4 can be replaced by a powerful microprocessor or a small PC with the necessary I / O modules installed. Therefore, the automatic operating system can be easily implemented by a powerful alternative control device.

此處PLC/ECU 100之一個可程式邏輯控制器(PLC)可利用RS-232或乙太網路來跟一台個人電腦(PC)相互連接與溝通，並且該CPU模組還可以跟多個輸入/輸出接口的模組連結溝通。此處整個系統的控制軟體是安裝在PC電腦裡，而PC可將一組預先校準好的設定點，下載到PLC的CPU中，然後CPU會將適當的控制信號傳發送到適當的I/O模組，再由控制器來實際執行控制動作。換句話說，一旦接口模組接收到某種控制信號，其可以用此信號來控制和監視泵、流量計/控制器、閥門、熱電偶、O2傳感器和 其他裝置的系統儀器及設備。同樣的，每個設備的狀態和傳感器的信號也可以傳輸到PLC，和經由反方向信號途徑傳回給個人電腦。 Here, a programmable logic controller (PLC) of PLC / ECU 100 can use RS-232 or Ethernet to connect and communicate with a personal computer (PC), and the CPU module can also communicate with multiple I / O interface module communication. The control software of the entire system is installed in the PC, and the PC can download a set of pre-calibrated setpoints to the CPU of the PLC, and then the CPU sends the appropriate control signals to the appropriate I / O. The module performs the control action by the controller. In other words, once the interface module receives a certain control signal, it can use this signal to control and monitor the system instruments and equipment of pumps, flow meters / controllers, valves, thermocouples, O 2 sensors and other devices. Similarly, the status of each device and the signals from the sensors can also be transmitted to the PLC and back to the personal computer via the reverse signal path.

本發明揭示之沼氣觸媒熱電共生機是一部自動操作可提供日常生活所需的熱氣、熱水及電的分散式能源供應機，其利用廚餘或***物經厭氧發酵後生成之沼氣，該沼氣進一步產生的熱能及電能之設備及方法，並且分散式發電也可以避免或降低因長途輸電之電力損失，是一種具有降低碳排放量功效的技術。 The biogas catalyst cogeneration unit disclosed by the present invention is a decentralized energy supply machine that can automatically operate to provide hot gas, hot water and electricity for daily life. It uses biogas generated from anaerobic fermentation of kitchen waste or excreta. The equipment and method for further generating heat and electric energy of the biogas, and the decentralized power generation can also avoid or reduce the power loss due to long-distance power transmission, and is a technology with the effect of reducing carbon emissions.

雖然本文揭示了示範性實施例，但應理解其可作其他變化，如此的變化並不被認為偏離本申請示範性實施例的精神和範圍，並且對於本領域技藝人士所有顯而易見的修改，皆包含於如下請求項的範圍內。 Although the exemplary embodiments are disclosed herein, it should be understood that other changes can be made. Such changes are not considered to depart from the spirit and scope of the exemplary embodiments of the present application, and all obvious modifications to those skilled in the art include Within the scope of the following claims.

1‧‧‧風能/太陽能發電系統 1‧‧‧wind energy / solar power system

100‧‧‧PLC/ECU 100‧‧‧PLC / ECU

2‧‧‧電網 2‧‧‧ Power Grid

3‧‧‧可編程序控制器/儲電池 3‧‧‧ Programmable controller / battery

4‧‧‧氫氣儲存槽 4‧‧‧Hydrogen storage tank

5‧‧‧電解槽 5‧‧‧ electrolytic cell

6‧‧‧啟動IC引擎及發電機 6‧‧‧Start IC engine and generator

7‧‧‧氧氣儲存槽 7‧‧‧ oxygen storage tank

8‧‧‧乾燥及吸附劑槽 8‧‧‧ drying and adsorbent tank

9‧‧‧觸媒重整反應器 9‧‧‧ catalyst reforming reactor

10‧‧‧沼氣儲存槽 10‧‧‧Biogas storage tank

11‧‧‧熱交換器 11‧‧‧ heat exchanger

12‧‧‧儲水槽 12‧‧‧ water tank

13‧‧‧熱水槽 13‧‧‧ hot water tank

14‧‧‧重整氣儲存槽 14‧‧‧ reformed gas storage tank

15‧‧‧內燃機/渦輪機 15‧‧‧ Internal combustion engine / turbine

16‧‧‧發電機 16‧‧‧ Generator

17‧‧‧熱交換器 17‧‧‧Heat exchanger

Claims (11)

一種沼氣觸媒熱電共生機，其包含：(a)一沼氣儲存槽；(b)一觸媒重整反應器，其包含總鉑族金屬在0.10至2000g/ft3之間顆粒狀受載型或非受載型鉑族金屬整體觸媒劑，且與該沼氣儲存槽相連接；(c)一氧氣儲存槽，與該觸媒重整反應器相連接；(d)一重整氣儲存槽，氣壓保持在1到100大氣壓之間，與該觸媒重整反應器相連接；(e)一內燃機/渦輪機和一發電機，連接於該重整氣儲存槽下方，以產生並供應電力；(f)二個熱交換器供應熱氣和熱水，第一熱交換器設置在該觸媒重整反應器與該重整氣儲存槽之間，第二熱交換器設置於該內燃機/渦輪機之後；及(g)一自動控制系統，其包含控制電腦和/或微處理器、流量計/控制器、閥門、泵、傳感器、溫度計、操作的控制軟體，使該沼氣儲存槽及該氧氣儲存槽提供在該觸媒重整反應器入口處的氧氣、水和沼氣之燃料混合氣，並保持O2/CH4比例在0.8以下，且(H2O+CO2)/CH4比例在10.0以下。 A biogas catalyst thermoelectric symbiosis machine, comprising: (a) a biogas storage tank; (b) a catalyst reforming reactor, which includes a granular platinum-type loaded type between 0.10 and 2000 g / ft 3 Or an unsupported platinum group metal monolithic catalyst and connected to the biogas storage tank; (c) an oxygen storage tank connected to the catalyst reforming reactor; (d) a reformed gas storage tank The gas pressure is maintained between 1 and 100 atmospheres, and is connected to the catalyst reforming reactor; (e) an internal combustion engine / turbine and a generator are connected below the reforming gas storage tank to generate and supply electricity; (f) Two heat exchangers supply hot gas and hot water, a first heat exchanger is disposed between the catalyst reforming reactor and the reformed gas storage tank, and a second heat exchanger is disposed after the internal combustion engine / turbine ; And (g) an automatic control system including control software that controls a computer and / or microprocessor, flow meter / controller, valve, pump, sensor, thermometer, and operation to enable the biogas storage tank and the oxygen storage tank Fuel mixture of oxygen, water and biogas provided at the entrance of the catalyst reforming reactor And keep the O 2 / CH 4 ratio below 0.8 and the (H 2 O + CO 2 ) / CH 4 ratio below 10.0. 如請求項1所述之沼氣觸媒熱電共生機，其中觸媒重整反應器包含至少一個蒸汽重整反應器、部分氧化重整反應器或自熱重整反應器，且該鉑族金屬觸媒為包含一種或多種選自由鉑(Pt)、鈀(Pd)、銠(Rh)、銥(Ir)、鋨(Os)及釕(Ru)所組成之群組之金屬，其為含有總鉑族金屬在0.10至2000g/ft3 之間的顆粒狀受載型或非受載型鉑族金屬觸媒。 The biogas catalyst thermoelectric symbiosis machine according to claim 1, wherein the catalyst reforming reactor comprises at least one steam reforming reactor, partial oxidation reforming reactor or autothermal reforming reactor, and the platinum group metal catalyst The medium is one or more metals selected from the group consisting of platinum (Pt), palladium (Pd), rhodium (Rh), iridium (Ir), osmium (Os), and ruthenium (Ru). Particulate supported or unsupported platinum group metal catalysts having a group metal between 0.10 and 2000 g / ft 3 . 如請求項1所述之沼氣觸媒熱電共生機，其中該沼氣儲存槽係先與一乾燥及吸附槽連接後，再連接至觸媒重整反應器。 The biogas catalyst cogeneration unit according to claim 1, wherein the biogas storage tank is connected to a drying and adsorption tank before being connected to the catalyst reforming reactor. 如請求項3所述之沼氣觸媒熱電共生機，其中該乾燥及吸附槽係進一步與一啟動IC引擎及發電機連接，且該啟動IC引擎及發電機連接亦與該觸媒重整反應器連接。 The biogas catalyst cogeneration unit according to claim 3, wherein the drying and adsorption tank is further connected to a start-up IC engine and generator, and the start-up IC engine and generator connection is also connected to the catalyst reforming reactor connection. 如請求項4所述之沼氣觸媒熱電共生機，其進一步包含一電解槽，該電解槽與一氫氣儲存槽及該氧氣槽連接，且該氫氣儲存槽與該啟動IC引擎及發電機連接。 The biogas catalyst cogeneration unit according to claim 4, further comprising an electrolytic cell, the electrolytic cell is connected to a hydrogen storage tank and the oxygen tank, and the hydrogen storage tank is connected to the start-up IC engine and the generator. 一種操作如請求項1至5任一項之沼氣觸媒熱電共生機之方法，其包含：提供一條或多條儲存在該控制電腦和/或該微處理器內的流量控制曲線，該流量控制曲線利用該各儲存槽內的壓力以同時控制在觸媒重整反應器入口處每種反應氣的流量、反應後重整氣的氣體成分和產量，並依據各儲存槽內的氣壓來調節流量，使沼氣儲存槽及該氧氣儲存槽提供在該觸媒重整反應器入口處的氧氣、水和沼氣之燃料混合氣，保持O2/CH4比例在0.8以下，且(H2O+CO2)/CH4比例在10.0以下，其中該各儲存槽之氣壓保持在1至100大氣壓之間、該觸媒重整反應器內的反應溫度保持在1200℃以下。 A method for operating the biogas catalyst cogeneration machine as in any one of claims 1 to 5, comprising: providing one or more flow control curves stored in the control computer and / or the microprocessor, the flow control The curve uses the pressure in each storage tank to simultaneously control the flow of each reaction gas at the entrance of the catalyst reforming reactor, the gas composition and output of the reformed gas after the reaction, and adjust the flow according to the air pressure in each storage tank. So that the biogas storage tank and the oxygen storage tank provide a fuel gas mixture of oxygen, water and biogas at the entrance of the catalyst reforming reactor, keeping the O 2 / CH 4 ratio below 0.8, and (H 2 O + CO 2 ) The ratio of / CH 4 is below 10.0, wherein the pressure in each storage tank is maintained between 1 and 100 atmospheres, and the reaction temperature in the catalyst reforming reactor is maintained below 1200 ° C. 如請求項6之方法，其進一步包含觸媒重整反應器之三階段反應：(a)第一階段，控制O2/CH4在0.08到0.25之間，觸媒重整反應器溫度在200℃到500℃之間，且在含0-5%(H2+水蒸氣)的情況下，將沼氣內所有的硫化合物在經過顆粒狀受載型或非受載型鉑族金屬觸媒時，全部 轉化硫化氫；(b)第二階段，利用一種或多種選自由鋅、鎳、銅、鈷、沸石、鐵、鋁、銅及鋅氧化物所組成之群組或混合氧化物做為硫化氫的吸附劑，並在200-500℃之間脫硫；(c)第三階段，利用第二階段的觸媒重整反應器，控制氧氣含量以提高O2/CH4比例，並提高沼氣中甲烷的反應轉換率和出口重整氣的產量。 The method of claim 6, further comprising a three-stage reaction of the catalyst reforming reactor: (a) in the first stage, control O 2 / CH 4 between 0.08 and 0.25, and the temperature of the catalyst reforming reactor at 200; ℃ to 500 ℃, and in the case of 0-5% (H 2 + water vapor), when all sulfur compounds in the biogas pass through the particulate supported or unsupported platinum group metal catalyst , All convert hydrogen sulfide; (b) the second stage, using one or more selected from the group consisting of zinc, nickel, copper, cobalt, zeolite, iron, aluminum, copper and zinc oxides or mixed oxides for sulfurization Hydrogen adsorbent and desulfurization between 200-500 ℃; (c) the third stage, using the catalyst reforming reactor in the second stage, controlling the oxygen content to increase the O 2 / CH 4 ratio and increasing the biogas Methane reaction conversion rate and output reformed gas output. 如請求項7之方法，其中第一階段係降低水蒸氣的含量來增加下游硫化氫的吸附劑吸附總量，以及利用氫和氧的反應熱來增加觸媒的溫度，並增加硫化合物和甲烷的觸媒部分氧化反應速度。 The method of claim 7, wherein the first stage is to reduce the content of water vapor to increase the total amount of adsorbent adsorbed by downstream hydrogen sulfide, and use the reaction heat of hydrogen and oxygen to increase the temperature of the catalyst, and increase sulfur compounds and methane. The partial oxidation rate of the catalyst. 如請求項7之方法，其中可使用選自由天然媒氣、液化媒氣、生質洒精、甲醇、汽油、柴油、生質柴油或可揮發的碳氫化合物，經由該觸媒重整反應器之操作，除去在燃料內所含的硫化合物，和產生含(H2+CO)的可燃重整氣供做內燃機/渦輪機的唯一燃料或供做稀薄燃燒的部份燃料。 The method as claimed in claim 7, wherein a catalyst selected from the group consisting of natural gas, liquefied gas, biomass spray, methanol, gasoline, diesel, biodiesel, or volatile hydrocarbons can be used through the catalyst reforming reactor This operation removes the sulfur compounds contained in the fuel, and generates combustible reformed gas containing (H 2 + CO) for the sole fuel of the internal combustion engine / turbine or part of the fuel for lean combustion. 如請求項9之方法，其中該選自由天然媒氣、液化媒氣、生質洒精、甲醇、汽油、柴油、生質柴油或可揮發的碳氫化合物，可用做備用或緊急時之燃料，並以請求項1之沼氣觸媒熱電共生機來供應熱水、熱氣及電。 The method of claim 9, wherein the method is selected from the group consisting of natural media gas, liquefied media gas, biodegradable concentrate, methanol, gasoline, diesel, biodiesel, or volatile hydrocarbons, and can be used as a backup or emergency fuel. The biogas catalyst cogeneration unit of claim 1 is used to supply hot water, hot gas and electricity. 如請求項7之方法，其中，控制重整器進口沼氣及氧混合氣的O2/CH4比例在0.08-0.50時，可控制並製造不同(H2+CO)/CH4比例的混合內燃機燃料，以做為稀薄燃料並提升沼氣內燃機/渦輪機的燃燒效率和降低其污染氣的排放量。 The method of claim 7, wherein when the O 2 / CH 4 ratio of the inlet biogas and oxygen mixture of the reformer is 0.08-0.50, the hybrid internal combustion engine with different (H 2 + CO) / CH 4 ratio can be controlled and manufactured. Fuel as a lean fuel to improve the combustion efficiency of biogas internal combustion engines / turbines and reduce their emissions of pollutants.
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TWI679342B (en) * 2018-11-01 2019-12-11 黃恆信 Catalytic biogas combined heat and power generator and method of desulfurization of hydrocarbon and bio-fuels using this catalytic biogas combined heat and power generator

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