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作者:賴宣宏、黃建誠、洪永杰(2005-06-26);推薦:徐業良(2005-06-29)

生質柴油製備技術專利地圖與專利分析

本文首先對生質能(biomass energy)生質柴油(biodiesel)之相關製備技術作一簡介,以對其整體技術發展現況有所瞭解。接著本文針對生質柴油之製備方法、設備與技術作專利分析,藉以瞭解現有產品的專利狀況以及技術特點,並利用專利地圖(patent map)的製作,將專利資訊做最有效之組織分析,以了解整體產業環境之發展。同時針對現有技術其開發動向、運用手法與其達成效進行交叉分析,以期在舊有技術領域中看出可開發的新區域,藉以擬定技術研發與創新設計之切入點,建立有別於現有產品之市場與技術區隔。

1.     生質能簡介

近年來由於二氧化碳等會造成溫室效應的氣體排放遽增,引起全球暖化現象,使得熱污染問題廣受重視,於是如何尋求新且潔淨的生質能以供未來使用,乃成為一個重要的議題。根據國際能源總署的統計,目前生質能是全球第四大能源,僅次於石油、煤及天然氣。生質能供應全球約14%的初級能源需求,也提供了開發中國家35%的能源,是目前最廣泛使用的再生能源。

生質能(biomass energy)是指利用生質物(biomass)經轉換所獲得的電與熱等可用的能源。生質物則泛指由生物產生的有機物質,例如木材與林業廢棄物(如木屑)、農作物與農業廢棄物(如黃豆莢、玉米穗軸、稻殼、蔗渣等)、畜牧業廢棄物(如動物屍體)、都市垃圾與垃圾掩埋場與下水道污泥處理廠所產生的沼氣、工業有機廢棄物(如有機污泥、廢塑橡膠、廢紙、造紙黑液等)。

生質能利用的技術範圍相當廣泛,其轉換為能源的方式可概分為直接燃燒技術、物理轉換技術、熱轉換技術、與化學∕生物轉換技術。

(1)   直接燃燒

直接燃燒技術是把廢棄物直接燃燒以產生熱能與電力,例如現有的大型垃圾焚化廠,以焚化垃圾發電。

(2)     物理轉換技術

物理轉換技術是把廢棄物經破碎、分選、乾燥、混合添加劑、及成型等過程,製成易於運輸及儲存的固態衍生燃料,以作為鍋爐、水泥窯的燃料,例如紙廠把廢棄物製成錠型的固態燃料,作為燃煤鍋爐的輔助燃料。

(3)   熱轉換技術

熱轉換技術是指把廢棄物利用氣化與裂解(液化)等熱轉換程序產生合成燃油或燃氣(瓦斯),作為燃燒與發電設備的燃料。例如從廢保麗龍或廢塑膠可回收燃油作為鍋爐的燃料;又如稻殼、能源作物或廢紙渣可產製合成燃氣,進行燃氣發電。

(4)   化學∕生物轉換技術

化學生物轉換技術,是指經醱酵、轉酯化等生物化學轉換程序以產生沼氣、酒精、生質柴油、氫氣等,作為引擎、發電機與燃料電池的燃料。例如垃圾掩埋場廢棄物、工業或畜牧廢水經醱酵產生的沼氣可以發電;又如廢食用油經轉酯化反應可產製生質柴油,作為汽車的替代燃料等。

將生質物轉化為類似煤、油、天然氣的衍生燃料,易於儲運且可提高能源效率,降低污染,同時亦可與資源回收系統結合,節省廢棄物處理成本,使生質能技術極具市場競爭力。以下繼續將對生質物轉換為生質柴油的製備技術進行簡介。

2.     生質柴油製造技術簡介

2.1 生質柴油製備

生質柴油係利用各種植物油脂製成,如大豆油(黃豆油)、玉米油、棕櫚油、或動物油脂,均可做為其原料。植物油脂係由90~95%的甘油酯(Glycerine)與脂肪酸(Fatty acid)組成,配合醇類(甲醇、乙醇)經轉酯化反應(Transesterification Reaction)製造,產物為脂肪酸甲酯(或乙酯)及甘油,因為兩者不互溶,甘油會沉在底部,上層便是脂肪酸甲酯,再以蒸餾去除未反應完全之油脂即得生質柴油,其中脂肪酸甲酯的運用性質與石化柴油非常接近。因生質柴油係由動、植物油脂製成,具有能源再生性、生物可分解性與低污染性,可減少空氣污染,且其性質與柴油接近可直接使用在柴油引擎上,或作為柴油燃料的添加劑,不需更改任何引擎設計與設備等優點,目前已成為世界各國積極發展的替代能源之ㄧ。

目前在利用植物油脂製備生質柴油的過程中,如何有效降低油脂的黏度以直接用於柴油引擎為重要的研究工作之ㄧ。為了降低黏度,常用的方法有稀釋(Dilution)、熱分解(Pyrolysis)、微細乳化(Micro-emulsion)、以及轉酯化(Transesterification)等技術方法予以達成。植物油脂的稀釋可使用柴油或溶劑(如醇類)等予以混合稀釋即可;熱分解方法則須另經高溫加熱裂解,猶如石油原油經裂解過程以產生柴油,甚為麻煩而且成本亦高;植物油脂的微細乳化過程係採用乳化劑,使液體(油脂)有效分散的系統,以利不易混合的液體(油脂)成為比膠體(Colloid)更微細的液體粒子,使之改善噴霧特性而易引起在引擎氣缸內點火燃燒,以提升引擎運轉效率。

現今生質柴油製備上,最好也最常用的方式是將植物油脂予以轉酯化,下一節將針對轉酯化技術進行細部介紹。

2.2 轉酯化(Transesterification)反應

轉脂化反應是目前最普遍的利用植物油做為車用燃料的方法,其反應方程式如圖1所示。基本上這是個簡單的化學反應,但必須在適當的觸媒存在下方能進行,為了增加產率,通常都會過量添加低碳數醇類,如甲醇或乙醇,醇類的碳數越少反應越容易進行。所用的觸媒是轉酯化反應最重要的關鍵,可用觸媒有強鹼(NaOHKOH等)、強酸(硫酸、鹽酸)、和生物觸媒。目前工業化的製程都為強鹼製程,因為強鹼製程反應快技術也最為成熟。但強鹼製程的缺點為反應物必須非常精純,必須無水,如有水分混入都會使反應轉為皂化反應,亦即形成令人頭痛的副產品脂肪酸納(肥皂)使整體轉化率降低與生質柴油回收純化困難。

1. 轉脂化化學反應過程

此外,原料油酯中的游離脂肪酸(Free fatty acid)含量不能太高,因為游離脂肪酸不會形成生質柴油,而會先與強鹼反應直接變為肥皂,同時造成強鹼不足的情形發生。原本估計反應所需的強鹼,因為與游離脂肪酸反應,變成觸媒的量不夠而無法完全反應,因此必須進行觸媒量的添加計算,即所謂的酸價補償,依照游離脂肪酸含量決定強鹼的添加量。一般來說,強鹼製程的原料(醇類與油脂合計)所含水分必須小於0.06%,油脂所含游離脂肪酸必須小於0.5%

水和游離脂肪酸的含量限制對於強鹼製程使用較便宜的原料來生產生質柴油造成困擾,因為完全無水的醇類成本相當高,尤其是乙醇,所以強鹼製程幾乎只能使用較便宜的甲醇做原料。從動植物壓榨出來的油脂難免含有游離脂肪酸,必須加以精緻純化;而油炸過的廢食用油同時含有水分與游離脂肪酸,更不能直接用強鹼製程轉化成生質柴油。如果要用強鹼製程則必須先對反應物加以純化,以去除水分和游離脂肪酸。

水分與游離脂肪酸含量過高的情形,可用強酸製程來處理,強酸製程的雜質容忍度較高,但反應複雜緩慢,幾乎沒有工業化的製程,但可考慮將強酸和強鹼製程串聯,先用強酸製程反應去除部分的雜質,純化後再進行強鹼製程,不過該種方式成本較高。因此目前工業界大規模量產生質柴油的方式多採用強鹼製程,以精緻的純植物油為原料。另外,轉酯化反應的副產品甘油,經分離純化後是一種高價值的產品,在醫療、化妝品、特用化學品、與國防工業上都有重要的應用。

2.3 生物觸媒轉酯化製造技術

以生物觸媒轉脂化開發生質柴油,是全球正在研發之新製程,利用生物觸媒進行生質柴油轉化生產主要分為胞外酵素(extracellular)和胞內酵素(intracellular)。利用胞外酵素進行的研究已相當多,Shimada[1999]等人測試不同脂肪分解酵素後發現,固定化(Candida Antarctica)脂肪分解酵素(Novozym 435)有最佳的甲醇解效率。不過利用胞外酵素最大的缺點在於酵素需經過分離與純化,程序複雜解經過處理的酵素通常較不穩定且昂貴,因此有許多研究進行利用整個細胞進行催化,Ban[2002]等人的研究指出,利用整個細胞生物觸媒固定化在多孔性生質載體(biomass support particles, BSPs)上,對生質柴油的量產具有很大潛力。

3.     生質柴油製備技術專利檢索策略

本文專利檢索的地區定為美國地區之專利資料。重視全球市場的企業,在規劃其專利佈局時,皆會投入技術較為先進、市場需求性高的美國地區,因此美國專利資料庫收納全球最重要、完整的專利資料,藉由此區專利資料的檢索與研究,可使本計畫之專利分析成果同時掌握廣度與深度、即時性、與發展性。

根據上述生質柴油的簡介,可以了解“biodiesel”“biofuel”為最常使用的英文名稱,因此本研究將以這兩組關鍵字及其相關變化詞,在專利名稱(Title)、摘要(Abstract)與專利申請範圍(Claim)中檢索,檢索日期至20041231止。由於各國專利權人所申請之專利多在美國有對應之專利,因此初步檢索範圍限制在USPTO中已公告的專利,之後再依據其國際專利技術分類碼(IPC)與美國專利技術分類碼(UPC)各種種不同的生質柴油製備與方法作一有效分類。為提高專利檢索之檢全率,本研究檢索時將採用關鍵字(“biodiesel”“biofuel”)聯集的方式來擴大檢索範圍,並配合人工逐篇專利評選以求達成較高的檢準率,表1為此次生質柴油製備技術美國專利檢索背景設定。

1. 生質柴油製備技術美國專利檢索背景設定

搜尋公司

不限

搜尋地區

美國

搜尋年份

~2004/12/31

搜尋欄位

專利名稱(Title)、專利摘要(Abstract)、專利範圍(Claims)、國際專利分類碼(IPC)

搜尋語言

英文

資料庫名稱

USPTO專利資料庫()Delphion專利資料庫(輔)

關鍵字

“biodiesel”“biofuel”

檢索語法

ABST/(“biodiesel” OR “biofuel” OR “bio-diesel” OR “bio diesel” OR “bio-fuel” OR “bio fuel”) OR TTL/(“biodiesel” OR “biofuel” OR “bio-diesel” OR “bio diesel” OR “bio-fuel” OR “bio fuel”) OR ACLM/(“biodiesel” OR “biofuel” OR “bio-diesel” OR “bio diesel” OR “bio-fuel” OR “bio fuel”) AND ISD/1/1/1971->31/12/2004

利用USPTODelphion專利資料庫交互檢索,得到生質柴油製備技術之美國公告專利共計211件,後續分析皆以已確認之美國公告專利為專利分析範圍。以下即針對此211件生質柴油製備技術之美國公告專利製作專利管理圖表。

所謂專利管理圖表即是初步專利書目資料的圖表陳列,其目的是能夠將所檢索出的專利作一簡單呈現,並提供爾後技術分析的初步參考。雖然管理圖表無法提供深一層的技術特徵,但是對於技術掌握與分佈可提供某種程度的了解。一般而言,管理圖表分析包括專利件數分析、生命週期曲線分析、競爭國家分析、競爭公司分析、發明人分析、國際專利分類(IPC)分析、與美國專利分類(UPC)分析等,將於以下各節分別討論。

4.     生質柴油製備技術專利件數分析

2為生質柴油製備技術歷年專利件數分佈,其中橫軸為申請日與公告日之時間軸,縱軸為專利件數。圖中藍色線代表以專利申請日分析,藉由申請日作分析,可以瞭解技術的萌芽時間;暗紅色線代表以專利公開日作分析,藉由公開日作分析可以得知最新的發展現況。

2. 生質柴油製備技術歷年專利件數

生質柴油製備技術最早專利是申請於1975年,初步分析其書目資料,可發現可發現專利名稱為水油操作流體的微乳化技術(Water-in-oil microemulsion drilling fluids),專利權人為Marathon Oil Company。檢視此篇專利可以發現,其技術內容為微乳化(microemulsion)的製造方法,利用改進操作流體的分子大小,來提高操作流體的工作特性。藉由申請日與公告日的比對,可以看出,生質柴油製備技術專利與一般專利相似,其申請時間與核准公告時間約有2~3年的差距。

生質柴油製備技術專利申請件數自1991年開始穩定成長,1999年申請件數達26件,藉由申請日與公告日的比對可以看出,生質柴油製備技術專利與一般專利相似,其申請時間與核准公告時間約有3年的差距,2002年以後申請案件許多尚未核准公告,因此未被檢索出來。生質柴油製備技術專利核准件數則每年持續增加,2001年核准件數達26件。

3與表2說明專利技術生命週期圖之意義,比對專利件數與專利權人數,可以推論此專利技術是處於萌芽期、成長期、成熟期、或技術瓶頸期。圖4為生質柴油製備技術專利技術生命週期圖(以兩年為計算單位),比對圖4與圖3可推論生質柴油製備技術專利技術仍處於技術成長期。

3. 技術生命週期圖示

2. 技術生命週期圖簡介

階段

階段名稱

代表意義

第一階段

技術萌芽

廠商投入意願低,專利申請件數與專利權人數皆少

第二階段

技術成長

產業技術有突破或廠商對於市場價值有了認知,競相投入發展,專利申請量與專利權人數急遽上升

第三階段

技術成熟

廠商投資於研發的資源不再擴張,只剩少數繼續發展此類技術,且其他廠商進入此市場意願低,專利申請量與專利權人數成長逐漸減緩

第四、五階段

技術瓶頸

產業技術研發遇瓶頸難以突破或此類產業已過於成熟,專利申請量與專利權人數呈現負成長

4. 生質柴油製備專利技術生命週期圖

5.     生質柴油製備技術專利國家別分析

3為生質柴油製備技術專利所屬國件數分析表。由表3可看出,投入生質柴油製備技術技術發展並在美國獲得專利之國家共有16國,總專利件數211件,專利權人共159位,其中美國、德國、日本與英國四國所獲得專利件數佔總專利件數之84.4%,是主導生質柴油製備技術技術之重要國家。

另外,由分析資料顯示,目前台灣在美國獲得生質柴油製備技術之相關專利有1(US6,398,707),其技術內容是利用轉酯化法製造生質柴油之技術(該專利詳細內容請參考附錄),與美德日英等技術先進國家比較,台灣於生質柴油製備技術技術發展上仍有相當大之空間。

4. 專利所屬國件數分析表

所屬國

專利所屬國

專利件數

專利權人數

件數百分比

US

美國

143

97

67.8%

DE

德國

13

8

6.2%

JP

日本

12

13

5.7%

GB

英國

10

9

4.7%

FR

法國

6

5

2.8%

SE

瑞典

5

5

2.4%

CA

加拿大

5

5

2.4%

FI

芬蘭

4

4

1.9%

NL

荷蘭

3

3

1.4%

IT

義大利

3

2

1.4%

AT

奧地利

2

2

0.9%

TW

台灣

1

1

0.4%

KR

南韓

1

1

0.4%

IL

以色列

1

1

0.4%

CH

瑞士

1

2

0.4%

BE

比利時

1

1

0.4%

合計

211

159

100%

6.     生質柴油製備技術專利權人(公司)分析

專利權人分析係針對特定之競爭對手進行相關競爭指標分析,藉以深入了解競爭對手之動向與研發能力。

6.1 公司研發能力比較

設定研發能力加權參數,計算技術競爭公司之「相對研發能力值」,可觀察各競爭公司研發能力之強弱。表5為生質柴油製備技術技術競爭公司相對研發能力值比較表,表中相對研發能力值是沿用專利分析軟體“Patent Guider”預設之加權參數(專利件數加權參數為1.2、被引證分析加權參數為1.4、自我引證分析加權參數為0.9)來做計算。生質柴油製備技術技術相對研發能力值最高第一名為「Exxon Chemical Patents Inc.」,其相對研發能力值為100%;其次為「U.S. Secretary of Agriculture(美國農業部)」與「Pioneer Hi-Bred International, Inc.(全美最具規模玉米種子的生產公司)」,其相對研發能力值分別為82%59%

5.競爭公司相對研發能力比較表(前十名)

公司名稱

相對研發能力值百分比

Exxon Chemical Patents Inc.

100

U.S. Secretary of Agriculture

82

Pioneer Hi-Bred International, Inc.

59

ARCO Chemical Company

57

Institut Francais du Petrole

51

Ethyl Corporation

43

Henkel Kommanditgesellschaft auf Aktien

36

Rentech, Inc.

27

Erner; William E.

27

Marathon Ashland Petroleum LLC

26

6.2 重要競爭公司研發能力詳細數據分析

6為利用專利件數、活動年期、發明人數、以及平均專利年齡等競爭指標,分析重要競爭公司投入生質柴油製備技術的發展狀況,藉以顯示競爭公司之投入資源及有效掌握競爭環境之重要資訊。以下先就各指標名詞簡單介紹:

(1)   活動年期

觀察各競爭公司在本專案技術內有專利產出之活動期,進而可得知各公司投入本技術領域之研發時間。

(2)   發明人

競爭公司投入本研究技術研發之發明人數分析,透過競爭公司在本專案技術研發人員投入之多寡,以評析該公司對本技術之企圖心與競爭潛力。

(3)   平均專利年齡

將各專利權年齡總和除以專利件數所得之值。平均專利年齡越短,表示該公司於本專案技術內享有較長期之技術獨占性優勢,反之亦然。為各國專利制度不盡相同,專利權期間也不相同。以美國專利權年限20年為例,若分析專案之平均專利年齡越短(例如3年),表示此專案之技術受專利權保護之時間將越長(還剩17年),享有較長期之技術獨占性優勢。

(4)   自我引證次數

本分析專案內公司引證自己公司之專利次數。

(5)   被其他人引證次數

本分析專案內公司之專利被其他公司引證之次數。

(6)   總引證次數

本分析專案內公司所擁有之專利自我引證次數加被其他人引證次數。

(7)   引證率

本分析專案內公司專利的總引證次數除以該公司專利件數的比值。引證率代表公司之每件專利產出被引用的次數,可用來衡量各競爭公司之專利產出品質。引證率越高的公司,表示該公司產出之專利平均被引用次數越多,顯示專利品質越高。一般評量先進公司之技術研發能力除可依專利件數多寡衡量外,引證率也是技術能力重要參考指標。利用引證率衡量公司之技術研發能力是屬於「質(quality)」的衡量指標,而專利產出件數則是「量(quantity)」的衡量指標。

(8)   技術獨立性

分析專案內公司引用自己公司專利的次數除以總引證次數之比值。技術獨立性表示公司技術研發內容與其他競爭公司的技術差異性。技術獨立性數值越高,表示該公司研發之技術獨特性較高(其研發路線較為獨立),同業間較少有公司追隨其技術研發,接近所謂的獨家技術;技術獨立性數值越低,表示該公司技術研發路線與其他競爭公司研發之技術內容相似程度較高,也較有技術侵權的可能性發生。

6. 相對研發能力前十名競爭公司之研發詳細數據

公司名稱

專利件數

活動年期

發明人數

平均專利年齡

自我引證次數

被其他人引證次數

總引證次數

引證率

技術獨立性

Exxon Chemical Patents Inc.

17

6

19

8

2

1

3

0.176

0.667

U.S. Secretary of Agriculture

7

5

11

16

0

16

16

2.286

0

Pioneer Hi-Bred International, Inc.

10

4

8

7

2

0

2

0.2

1

ARCO Chemical Company

4

4

8

13

1

12

13

3.25

0.077

Institut Francais du Petrole

4

4

11

15

1

10

11

2.75

0.091

Ethyl Corporation

6

5

7

10

2

2

4

0.667

0.5

Henkel Kommanditgesellschaft auf Aktien

4

4

17

13

0

5

5

1.25

0

Rentech, Inc.

2

2

3

12

0

6

6

3

0

Erner; William E.

1

1

1

25

0

8

8

8

0

Marathon Ashland Petroleum LLC

4

2

5

4

2

0

2

0.5

1

註:引證率及技術獨立性之平均值分別為1.020.05

觀察投入生質柴油製備技術之重要競爭公司專利詳細資料表(表6),可得知在本專利技術相關領域中,以Exxon Chemical Patents 公司專利之產出最多(17件),佔專利總數之8.1%,為投入生質柴油製備技術專利技術研發最活躍的公司。

Exxon Chemical Patents Inc.之專利產出共計17件,專利產出數量位居第一,專利活動年期有6年,投入之發明人數達19位,為目前投入最多研發人員之公司。平均專利年齡8年,屬為短、中期專利。在技術研發能力方面,Exxon Chemical Patents Inc.17件專利被引證總次數僅有3次(其中自我引證次數2次,被其他人引證次數1次),引證率為0.176,遠低於本研究平均引證率1.02甚多;技術獨立性則為0.667,高於本研究平均技術獨立性0.05,表示該公司技術研發內容與其他競爭公司的技術差異性較大。

美國農業部(U.S. Secretary of Agriculture)在生質柴油製備技術之研發共計有5個活動年期,投入之發明人達11位;平均專利年齡16年,多為中、長期專利,顯示對此產業耕耘已久。在技術研發能力方面,美國農業部7件專利被引證總次數高達16次(其中自我引證次數0次,被其他人引證次數16次),引證率為2.286,高於本研究平均引證率1.02甚多,顯示該群專利極有可能為核心技術專利;技術獨立性則為0,低於本研究平均技術獨立性0.05,表示其研發之技術與目前主流技術較為接近,與市場技術差異性不大。

另外值得注意的研發單位(人員)包括獨立發明人Erner; William E.,雖然其專利件數僅有1件,但其專利引證率高達8,顯示該專利極有可能為核心技術專利,值得詳細研究其所屬專利的技術內容。另外Pioneer Hi-Bred International, Inc.Marathon Ashland Petroleum LLC兩間公司之專利技術獨立性皆為1,高於本研究平均技術獨立性0.05甚多,顯示其研發之技術有別於目前主流技術,與現有市場技術差異性較大。

6.3 重要競爭公司歷年專利件數分析

5為上述生質柴油製備技術重要競爭公司歷年專利件數分析,可顯示主要競爭公司歷年在此一研發領域之投入概況。由圖5可看出,生質柴油製備技術專利產出件數最高的Exxon Chemical Patents公司,自1989年即有第一件專利產出並相繼於1997~2003年間產出專利,2001年產量達到高峰(8件)。

美國農業部在生質柴油製備技術專利技術領域投入發展相當早,1977年即有第一筆相關專利產出,之後於1984年(2件)與1996~2002年間陸續產出專利。Pioneer Hi-Bred International, Inc.的專利則密集於1999~2001年間產出,分別2件、2件與5件,專利產出速度相當快,惟2002年後並無專利產出,後續動態值得持續觀察。

反觀獨立發明人Erner; William E.在生質柴油製備專利技術領域於1982年即有第一筆相關專利產出,之後專利產出狀態呈現停滯。

5. 重要競爭公司歷年專利件數圖

7.     生質柴油製備技術專利重要發明人分析

本節針對生質柴油製備技術專利領域內具專利產出之重要發明人進行相關分析,包括重要發明人之專利產出數量、任職公司資訊、與歷年研發專利產出之情形等。

在本研究之生質柴油製備專利技術領域中,共有410位發明人。表7之重要發明人分析列出本專案技術領域之重要發明人、任職公司及個人專利產出件數。其中Caprotti; RinaldoJackson; GrahamLedeore; Christophe同屬Exxon Chemical Patents Inc.,但三人專利重疊性不高;另外Cole; Glenn S.Pioneer Hi-Bred International, Inc.的主要發明人,該公司10篇專利中有6篇出自其手。

7. 重要發明人分析

發明人

所屬公司

專利產出件數

Caprotti; Rinaldo

Exxon Chemical Patents Inc.Infineum USA L.P.

10

Cole; Glenn S.

Pioneer Hi-Bred International, Inc.

6

Jackson; Graham

Exxon Chemical Patents Inc.

5

Ulrich; James F.

Cargill, Inc.Renessen LLC

4

Ledeore; Christophe

Exxon Chemical Patents Inc.Infineum USA L.P.

4

Caprotti; Rinaldo為此項技術領域內擁有最多專利成果者,其專利歷年產出件數共10件,專利取得年份分佈(圖6)於1998~2004年間,並於2001年達到高峰(5件)。另外,第二名的發明人Cole; Glenn S.,專利歷年產出件數共6件,其專利取得年份介於1995~2001年間,Pioneer Hi-Bred International, Inc.之第一篇專利(US5,461,171)為其發明,惟2002年後並無專利產出。其餘發明人之專利皆集中於2001年開始陸續產出。

6. 重要發明人歷年專利件數分佈

8.     生質柴油製備技術專利之IPC分析

8.1 IPC之意義

國際專利分類(International Patent Class, IPC),是世界智慧財產組織(World Intellectual Property Organization, WIPO)制訂的一種分類系統,可提供各國專利文獻統一分類之依據,其中包括了部(section)、主類(class)、次類(subclass)、主目(main group)、及次目(subgroup)五個階層,專利審查委員在閱讀專利說明書後,會依據該專利的技術特徵,賦予一個或多個的專利分類,以利分析者進行專利檢索。

IPC並非一成不變,而是會隨著技術演變進行調整,目前IPC最新版本是200011公佈的第七版,共有8個部、120個主類、628個次類、與大約69,000個目,編排架構說明如下:

(1)   (section)

「部」為IPC之主要分類大項,其所呈現的是發明專利領域之知識體系,部的名稱可視為是對該部內容之廣泛指示,且每個名稱後面都有一個主要細部展開項目之摘要類目。目前IPC將整個專利發明的知識分為8部,以大寫字母AH分別表示之,如表8

8. 8部的類目

類目名稱

A

生活必需品

B

處理操作;運輸

C

化學;冶金

D

纖維;紙

E

固定構造物

F

機械工程;照明;加熱;武器;爆破

G

物理學

H

電學

(2)   主類(class)

「主類」係由各部之下再細分為類,主要是針對該領域之發明技術作出更明確的定義與意涵。類的記號是在部的記號後加上兩位數字作為代表(如C10),而每一類名稱標示該類所包含的內容。

(3)   次類(subclass)

每類之下均包含一個或多個次類,其所指示的範圍比類更為特定與詳細,亦即次類比類更接近其所指涉之發明技術內涵。次類之記號為類的記號後面再加上一個大寫字母(如C10L),其名稱則為能夠正確指示該次類內容的名詞。

(4)   (group)

次類之下則再細分為多個目,較次類更能顯示特定範圍的專利技術。目又分為主目與次目;其中主目是為定義在檢索目的上有用的技術主題範圍,因此其記號顯示格式為次類字母計號之後加上13位數字、斜線及數字00組成(如C10L1/00)。

(5)   次目(subgroup)

次目是主目下的細分類,其記號是在目的記號後面(斜線後面)加上至少兩位不等於00的數字(如C10L1/18)。由於IPC採用十進位分類,因此任何斜線後的第3位或後續數字應被視為是前行數字的十進位細分數字,如3/426介於3/423/43之間。次目之名稱,則是限定在主目的範圍之內,利於定義檢索的技術主題範圍,而名稱之前有顯示該層次位置的一個或數個圓點,在所有情形下,次目名稱必須以從屬並受限於其上主目之名稱的方式來解讀。

9為生質柴油製備技術專利之IPC範例。每一個IPC均對應一個代表該分類的技術內容,IPC分析可對專利技術類別進行分析,包括IPC專利分類分析、IPC專利技術歷年件數分析、競爭國家分析與競爭公司分析等。利用IPC分析可以幫助分析者找出技術的主要領域和未開發領域,以作為研發方向的參考。

9. 生質柴油製備技術專利IPC範例

C10L1/18

說明

部之記號、名稱

C:化學;冶金

類之記號、名稱

10:石油、煤氣及煉焦工業;含一氧化碳之工業氣體;燃料;潤滑劑;泥煤

次類之記號、名稱

L:液化石油氣,為減少煙霧或不需要的積垢,或為易於除去煙灰而加入燃料或火中之添加劑

目之記號、名稱

1/00:液體含碳燃料

一點次目之記號、名稱

含添加劑者

二點次目之記號、名稱

‧‧有機化合物

三點次目之記號、名稱

‧‧‧含氧者

C10L 1/18應解讀成「液體含碳燃料中含氧之有機化合物添加劑」

8.2 生質柴油製備技術專利之IPC專利分類分析

10列出生質柴油製備技術專利四階IPC分析前三名的技術分類及內容。每件專利大多並非只有一個IPC四階分類號,因此表10中之專利件次是代表共有多少專利件次屬於該分類,例如US6,652,609號專利IPC分類為C10L1/18C10L1/24,因此共有2專利件次屬於C10L1分類。由表10中可得知C10L1A01H5C12P7此三項分類為生質柴油專利的重點領域,其中又以C10L1「液體含碳燃料」專利件數明顯較多。

10. 生質柴油製備技術專利四階IPC分析前三名的技術分類及內容

IPC分類

技術分類意義

專利件次

C10L1

液體含碳燃料

106

A01H5

新植物或獲得新植物之方法;通過組織培養技術之植物,如被子植物

19

C12P7

發酵或使用之方法以合成所要求的化合物或組合物或由外消旋混合物內分離光學異構物,如含氧有機化合物之製備

19

由於四階IPC之分類技術主題範圍較為粗略,因此將IPC向下延伸一階來作分類探討。表11列出生質柴油製備技術專利五階IPC分析前兩名的技術分類及內容,可以得知C10L1/18C10L1/22項分類為生質柴油製備技術專利的重點領域,其中又以C10L1/18「液體含碳燃料中含氧之有機化合物添加劑」專利件數較多。

11. 生質柴油製備技術專利五階IPC分析前二名的技術分類及內容

IPC分類

技術分類意義

專利件數

C10L1/18

液體含碳燃料中含氧之有機化合物添加劑

51

C10L1/22

液體含碳燃料中含氮之有機化合物添加劑

22

在此次的專利檢索中,由於五階IPC分類仍無法明確敘述相關之生質柴油的製備方式與其化學組成,因此以下將利用UPC(美國專利技術分類號)來協助分析。

9.     生質柴油專利之UPC分析

9.1 UPC之意義

雖然目前多數國家之發明專利均依據國際專利分類表予以分類,但美國仍舊採行其獨有之「美國專利分類表(United States Patent Classification, UPC)」。主要原因是UPC較為詳細,且修訂頻率較高。相較於IPC69,000多個主目與次目,UPC約有150,000的次類;IPC每五年修訂一次,而UPC則是每兩年修訂一次,更能符合科技進步與時代變遷之需求。

UPC編排體制是以「類」與「次類」兩個層次予以編排,彼此上下相互隸屬,編排架構說明如下:

(1)   (class)

UPC的第一層次為「類」,在每類之前均有說明其主題的「標題」,並以一組13位數的號碼表示該類。在類的範圍中,除部份尚未完全修訂外,每一類均有其定義說明(但新式樣專利的類別則無說明)。此定義可以說明每一類的主題範圍,比簡短的標題更容易清楚表達該類所涵蓋的技術主題範圍,例如類號044的定義說明為「燃油組成」、388的定義說明為「燃油:含氮、氧有機物」。

(2)   次類(subclass)

類之下再細分為次類,係針對該類主題範疇再予以劃分。次類同樣以號碼表示,且與類的號碼間隔有一條斜線。由於UPC採類與次類的二階分類方式,因此一個完整的UPC分類號應同時包括類與次類的號碼,例如在「102/301」的類號中,102代表「類」,而301代表針對該類細分的「次類」。

12為生質柴油專利之UPC範例。與IPC分析相同,每一個UPC均對應一個代表該分類的技術內容,UPC分析可對專利技術類別進行分析,包括UPC專利分類分析、UPC專利技術歷年件數分析、競爭國家分析與競爭公司分析等。

12. UPC編排架構內容示範

044/388

說明

類之記號、名稱

044:燃油及其相關組成

次類之記號、名稱

388:含酸脂之燃油

044/388」之化學組成為

9.2 生質柴油專利之UPC專利分類分析

13列出一階UPC分析前兩名的技術分類及內容,可得知044435此兩項分類為生質柴油專利的重點領域。與IPC相同,每件專利大多並非只有一個UPC一階分類號,因此表13中之專利件次是代表共有多少專利件次屬於該分類,例如US6,821,307號專利其UPC分類為044/347044/348,因此共有2專利件次屬於044分類。

13. 生質柴油專利主要UPC一階分類及內容

UPC分類

技術分類意義

專利件數

044

燃油和相關組成

239

435

分子生物學與微生物學

171

由於一階UPC之分類技術主題範圍較為粗略,因此將UPC向下延伸一階來作分類探討。表14列出二階UPC分析前五名的技術分類及內容,可以得知「含酸脂之燃油」、「脂類油」、「聚酯、半酯類燃油」、「酒精或酚醛羥的有機化合物」與「多細胞性生物」等五項分類為生質柴油專利的重點領域。圖8為此五項分類歷年專利件次分析,五項分類專利件數是呈現緩慢同步成長。這個整體趨勢可以看出生質柴油細部專利技術重點,「轉酯化技術」與「燃油合成製造」兩種常見的生質柴油製備技術仍然持續發展,而由多細胞性生物提取或製造生質柴油原料的加工處理技術,近年來的專利件數有逐漸成長的趨勢。

14. 生質柴油專利主要UPC二階分類及內容

UPC分類

技術分類意義

專利件數

化學組成

044/388

酸脂之燃油

19

435/134

脂;脂類油;高級脂肪酸;被氧化的油或油脂

14

 

044/389

聚酯、半酯類半酸化合物燃油的相關組成

13

554/167

包含酒精或酚醛羥的有機化合物組成

10

 

800/322

多細胞性生物的加工處理程序

10

 

 

8. 重要二階UPC專利技術歷年件次分析圖

9.3 生質柴油專利競爭國家與公司重要UPC專利件次分析

9為競爭國家重要UPC專利件次分析,比較專利數前三名之主要競爭國家(美國、德國與日本)在生質柴油專利主要二階UPC分類的專利分布情形。由圖中觀察可知,美國於044/388(含酸脂之燃油)、044/389(聚酯、半酯類半酸化合物燃油的相關組成)、800/322(多細胞性生物的加工處理程序)分類皆與德國、日本有較大幅度之領先;德國之UPC分類專利分布則較為平均;而日本則較集中於435/134(脂;酯類油)分類技術的研究。

9. 競爭國家重要UPC專利件次分析

10為競爭公司重要UPC專利件次分析,圖中顯示相對研發能力前十名之重要公司在在上述主要二階UPC分類的專利分布情形。Exxon Chemical Patents Inc公司專利件數較集中於044/389此類(聚酯、半酯類半酸化合物燃油的相關組成)Pioneer Hi-Bred International, Inc.公司專利件數較集中於800/322(多細胞性生物的加工處理程序)此類技術之研發,其餘公司之專利技術發展則多分布於044/388(含酸脂之燃油)的技術領域上。

10. 競爭公司重要UPC專利件次分析

10.    生質柴油製備技術之重要引證專利分析

15與圖11分別為生質柴油製備技術專利交互引證前七名之列表(取交互引證數達5以上之專利)與其相互引證族譜圖,所謂「交互引證數」的定義即為211件專利中引證此篇專利的專利數。例如,US4,695,411的交互引證數為9,即是211件專利中有9件專利引證此件專利。需要強調的是交互引證數的比較並不一定公平,因為越早公告之專利,被引證的機率就越高,但是在客觀上仍可初步瞭解哪些專利是相對重要的。從這7件專利所引伸出之引用關係,可以看出這些專利其關連性可分為六個技術類群:A類是含酸脂類之生質燃油製備技術(圖12),B類是含酒精或酚醛羥有機化合物之生質柴油製備技術(圖13),C類是植物油脂微細乳化製造技術(圖14),D類是具有鏈烷或烷烴(Alkanol)生質柴油的製備技術(圖15),E類是具有乙醚(Ether) 成分的燃油製備技術(圖16),F類則是利用三酸甘油脂製備生質柴油的技術(圖17)。其中US4,695,411US4,364,743US5,525,126US4,083,698US5,578,090US5,308,365、與US44512657篇專利為領先專利(母專利),在圖中以非淺綠底標示出來(淺綠底皆為子專利),這些專利分別帶領上述6個技術類群。我們利用Knowledgist軟體,針對此7篇重要母專利分析並整理包含專利標題、應用、目標、方法、特徵等重要資訊於附錄中,供研究人員參考。

15.生質柴油製備技術專利交互引證前六名

專利號

交互引證數

自我引證

被他人引證

專利權人

申請日

公告日

US4695411

9

0

9

Institut Francais du Petrol

1986/2/18

1987/9/22

US4364743

8

0

8

Erner; William E.

1980/6/17

1982/12/21

US5525126

7

0

7

Agricultural Utilization Research Institute

1994/10/31

1996/6/11

US4083698

6

0

6

Fuel Systems, Inc.

1976/12/1

1978/4/11

US5578090

6

0

6

BRI

1995/6/7

1996/11/26

US5308365

6

0

6

ARCO Chemical Company

1993/8/31

1994/5/3

US4451265

5

0

5

U.S. Secretary of Agriculture

1981/4/21

1984/5/29

11. 生質柴油製備技術重要專利引證族譜圖

12. 酸脂類之相關生質燃油製備技術

13. 含酒精或酚醛羥有機化合物之生質柴油製備技術

14. 植物油脂微細乳化製造技術

15. 具有鏈烷或烷烴(Alkanol)生質柴油的製備技術

16. 具有乙醚(Ether) 成分的燃油製備技術

17. 利用三酸甘油脂製備生質柴油的技術

11.    結論

本文完成了生質柴油製備技術之美國公告專利檢索與分析,並繪製完成基本管理圖表。生質柴油專利件數前四名國家為美國德國、日本與英國,合計佔總件數之84.4%。重要競爭公司為美國的Exxon Chemical Patents 公司、美國農業部Pioneer Hi-Bred International, Inc.ARCO Chemical Company。以應用領域而言,經由二階UPC專利分類分析可發現,044/388(含酸脂之燃油)為本研究之技術密集區(19件次),其次為435/134(脂;脂類油;高級脂肪酸;被氧化的油或油脂)有14件次。

IPCUPC分析可以看出生質柴油專利技術重點演變,「轉酯化技術」與「燃油合成製造」兩種常見的生質柴油製備技術仍然持續發展,而由多細胞性生物提取或製造生質柴油原料的加工處理技術,近年來的專利件數有逐漸成長的趨勢。此外由生質柴油之重要引證專利分析,分別找出了轉酯化與微乳化之源頭與基礎專利。同時本文利用Knowledgist軟體,針對源頭與基礎專利分析並整理相關重要技術資訊於附錄中,供研究人員參考。

參考資料

Shimada, Y., Watanabe, Y., Samukawa, T., Sugihara, A., Noda, H., Fukuda, H., Tominada, Y., 1999, “Conversion of vegetable oil to biodiesel using immobilized Candida antarctica lipase,” J. Am. Oil Chem. Soc., Vol. 76, pp. 789-793.

Ban, K., Hama, S., Nishizuka, K., Kaieda, M., Mastumoto, T., Kondo, A., Noda, H., Fukuda, H., 2002, “Repeated use of whole-cell biocatalysts immobilized within biomass support particles for biodiesel fuel production,” J. Molec. Catal. B, Enzymatic Vol. 17, pp. 157-165.

吳文騰,生物產業技術概論,民92,國立清華大學出版社。

陳達仁、黃慕萱,專利資訊與專利檢索,民91,文華圖書館管理資訊有限公司。

簡國明、洪長春、吳典熹、王永銘、藍怡平,奈米二氧化鈦專利地圖與分析,民92,行政院國家科學委員會科學技術資料中心。

鄭凱安、馬仁宏、林殿琪、黃郁棻、劉瑄儀,量子光點應用專利地圖與分析,民92,行政院國家科學委員會科學技術資料中心。

附錄

US 4,695,411

標題:Process for manufacturing a composition of fatty acid esters useful as gas oil substitute motor fuel with hydrated ethyl alcohol and the resultant esters composition

應用:The invention concerns a process for manufacturing a composition of fatty acid esters useful as gas oil substitute motor fuel, said composition containing at least one hydrated ethyl alcohol. The composition of the invention can be used for combustion in Diesel engines. The invention concerns a new process for manufacturing a fatty acid ester composition comprising a major portion of ethyl esters useful as gas oil substitute motor fuel, the raw materials consisting of oil or a grease of vegetable or animal origin and of one or more alcohols, mainly hydrated ethyl alcohol. The process described according to the invention is also applicable to fatty acid esters obtained from mixtures comprising ethyl alcohol, water and one alcohol selected from methyl, propyl, linear or branched butyl alcohols. 

目標:On the other hand, after purification, it is desirable that the yield by weight of raw esters, in proportion to the oil and irrespective of the alcohol content in the ester phase, be at least equal to 95% and preferably from 97 to 102%. One object of the present invention is hence to provide an economical process for manufacturing a mixture of esters of high purity and yield, useful as gas oil substitute motor fuel, from hydrated alcohol. Another object of the invention is to provide a process which can be applied not only with the use of neutral, weakly acid or degummed oils or greases but also with acid or very acid oils or greases. Another object of the present invention is to provide a process which can be directly applied to the manufacture of esters from seeds by using an extraction solvent, and also as a reactant, ethyl alcohol which, in contact with the seeds, may be more or less hydrated.

方法:In order to meet these objects, the invention provides a process for manufacturing a composition of fatty acid esters comprising a major proportion of ethyl esters usable as gas oil substitute motor fuel, by transesterification of an oil and/or grease of vegetable or animal origin optionally containing free acids; this process comprises: (a) a first step comprising at least one transesterification of said oil or grease in the presence of at least one monoalcohol consisting at least in major part of ethyl alcohol, said ethyl alcohol containing 1 to 60% by weight of water, and of an acid catalyst, said transesterification leading to the formation of a phase of high ester content and a phase of relatively high glycerol content, said first step being conducted in such conditions as to obtain a substantial conversion of oil or grease, (b) a second step wherein, after removal of the glycerol phase, the initial acidity, or the acidity formed during the first step, of the ester-containing phase is decreased to a value of at most about 2%; and (c) a third step wherein the phase resulting from the second step is subjected to at least one transesterification in the presence of at least one alcohol and of a basic catalyst, said transesterification leading to the formation of a phase containing mainly esters which are recovered and an alcohol phase, the alcohol being an aliphatic, The ester still contains alcohol and water when using a process of the ion exchange type except when dry methanol is used in the second and third steps according to the invention, no water addition being then required for settling. The upper ester phase comprises the ester, the alcohol, water traces and free acid corresponding to 2.5% of oleic acid. The ester still contains 5.3% of alcohol which has the composition of a water-alcohol azeotrope

特徵:The same hydrated alcohol in the presence of oil normally does not provide for a good conversion rate. However, the presence of alcohol up to 20% by weight does not disturb the operation of an engine although the cetane number is decreased. As soon as the temperature reaches 93. degree. C., 114 g of alcohol containing 50% of water are continuously introduced in such a manner as to maintain the temperature substantially constant.

 

US 4,364,743

標題:Synthetic liquid fuel and fuel mixtures for oil-burning devices

應用:The present invention relates to fuels as energy sources for oil- burning devices such as diesel engines, jet engines, turbines, and heating furnaces such as used in the home, and, more particularly, to synthetic or substitute fuels which can replace or be used in combination with known fuel sources. The present invention is directed to a novel fuel source for oil- burning devices such as diesel engines, jet engines, turbines, and home heating furnaces, which is a fuel in and of itself or can be mixed with presently available petroleum middle distillates.

目標:Accordingly, there is a need for a fuel which will preserve or extend the supply of petroleum middle distillates to meet the increasing demand for these fuel-efficient products. Therefore, the esters of the invention not only provide a means for conserving diminishing supplies of middle distillates when mixed therewith, but also provide a substitute for such distillates and a new energy source. 

方法:Examples of the esters of formula (I) that may be employed in the present invention include: (1) Methyl laurate, methyl myristate, methyl palmitate, methyl oleate, methyl elaidate, methyl linoleate, methyl linolenate, methyl stearate, methyl erucate, methyl ricinoleate, methyl licanate, methyl elaeostearate, methyl arachidonate, and methyl clupanodonate. Esters are preferably prepared by a transesterification reaction using various oils such as soya oil, palm oil , safflower oil, peanut oil, corn oil, cottonseed oil, linseed oil, oiticica oil, tung oil, coconut oil, castor oil, perilla oil, rapeseed oil, sunflower oil, lard, tallow, fish oils, blubber, lipids from marine and land animals and lipids from vegetable sources. Actual driving tests, using various types of fuels and fuel mixtures of the invention, were conducted using a 1979 Volkswagon diesel Rabbit automobile having a four-speed transmission (TEST CAR). The fuel representing the esters of the present invention was a mixture of esters containing by weight 

特徵:The esters of the present invention are commercially available or may be prepared by known methods such as transesterification of certain oils or esterification or epoxide addition of free fatty acids derived from such oils. Therefore, if these types of fuels can be mixed together with the esters of the present invention, the supply can be extended while obtaining more efficient use of the fuels. It has also been found that, where the esters of the invention alone are employed as a fuel, such as in diesel automobiles, such fuel provides greater efficiency by obtaining more miles per gallon consumed. The above results show that the esters of the invention not only burn clearner than ordinary diesel fuel, but also burn longer and are more efficient as a fuel source. 

 

US 5,525,126

標題:Reducing dislocations in semiconductors utilizing repeated thermal cycling during multistage epitaxial growth

應用:The present invention relates to a process for producing esters for use as a diesel fuel substitute using a nonalkaline catalyst. This embodiment is useful for feedstocks having a very high concentration of free fatty acids, such as acidulated soybean soapstock.

方法:The present invention includes a process for producing esters from a feedstock that includes a fat or an oil. The process includes mixing the feedstock with an alcohol and a catalyst. The process includes mixing the feedstock with an alcohol and a catalyst to form a reaction mixture. The process of the present invention is a great improvement over existing processes for making esters, particularly from feedstocks having fats or oils that contain a high concentration of free fatty acids, diglycerides and monoglycerides and impurities. The alcohol used in the process of the present invention is preferably a straight chain alcohol within a range of C.sub.1 -.sub.5. 

特徵:This process is unique with respect to a conversion of high free fatty acid oil to oil with less than 10% free fatty acids by weight in a single step. The process of the present invention produces esters from feedstocks having oil with a high free fatty acid content, such as 50% by weight, to make a mixture of esters and fatty acids in a ratio of about 96:4 by weight. By recycling the product to a reaction kettle, a crude methyl ester reaction product can be obtained having a free fatty acid content of about 0.8% by weight or even less. Further, the transesterified mixtures have properties that fall within a range of physical properties of a mineral diesel oil without further treatment, such as distillation. However, the water does not diminish the effectiveness of the catalyst. Feedstocks of materials such as degummed soy oil and once refined soy oil, are also transesterified in the process of the present invention to make a mixture having a low concentration of free fatty acids in the methyl ester reaction mixture, of about 0.4% to 0.2%. 

 

US 4,083,698 

標題:Clear and stable liquid fuel compositions for internal combustion engines

應用:This invention relates to clear and stable fuel compositions, preferably for use in internal combustion engines, but which may be used for any purpose requiring a combustible hydrocarbon fuel, including domestic and industrial heat and power. More particularly, this invention relates to the preparation of clear and stable liquid fuel compositions comprising (a) a mixture of hydrocarbons, such as gasoline, diesel fuel, or fuel oil; (b) water; (c) preferably a water-soluble alcohol; and (d) a combination of surface-active agents. The clear, stable liquid fuel containing the water, water-soluble alcohol, and surface-active agents has a low viscosity, like the hydrocarbon fuel itself, thereby making it particularly adaptable for storage in stationary fuel tanks and for transport and utilization in conventional carburetor systems. Mixtures are particularly useful in broadening the types of materials used in making the W/O emulsions. 

目標:An important objective of this invention is to provide a fuel for the internal combustion engine which results in significant decreases of toxic exhaust gases or vapors without sacrificing engine performance or efficiency. Accordingly, our invention is the discovery of certain combinations of surface-active agents which will bring both the alcohol, water, water-soluble constituents, and the hydrocarbon fuel constituent into complete phase, resulting in a clear, stable liquid fuel for a variety of uses including use in internal combustion engines. The purpose of the water in the fuel is to provide a lower temperature and broader temperature-time profile during the combustion of the fuel. The purpose of the water-soluble alcohol, such as methanol, is to provide anti-freeze characteristics to the fuel, thereby resulting in a liquid fuel stable below the freezing point of water. 

方法:All of these W/O emulsions when prepared at room temperature were clear. The sludge contains numerous small crystalline-appearing particles when the control is removed from the freezer. Examples Using Oleic Acid With Various Non-Ionic Surfactants for W/O Emulsions With Diesel Fuel Examples Using Linoleic Acid (Emersol 305) With and Without Cyclohexanol/Cyclohexanone for W/O Emulsions With Diesel Fuel. 

特徵:These emulsions can tolerate further additions of methanol and also water and still maintain excellent stability at both room temperature and low temperature. In practically all cases when clear emulsions were formed at room temperature, the clarity was actually significantly better than the control diesel fuel which has a characteristic slight haze. All of the emulsions listed in the table were as good or better than the control. The stability of the emulsion with this 1:2 ratio and having sufficient water is also good at -24.degree. C. They were completely clear at room temperature and showed excellent stability at low temperature compared to the control.  

 

US 5,578,090 

標題:Biodiesel fuel

應用:This invention relates to biodiesel fuels, which are blends of petroleum-based diesel fuel and fuels derived from biological, renewable sources. The resulting product is suitable for blending with diesel fuel to form an alternative fuel composition. The fuel additive composition prepared as described above can be used directly in a diesel engine, or can be blended with petroleum-based diesel fuel at a ratio such that the resulting alternative fuel composition contains between approximately 25 to 95 percent diesel fuel and between approximately 5 to 75 percent of the fuel additive composition. Modifications and variations of the present invention relating to a fuel additive composition and an alternative fuel derived from the composition will be obvious to those skilled in the art from the foregoing detailed description of the invention. 

目標:There remains a need for an improved fuel derived from renewable sources that can be blended with diesel fuel, and that does not damage an engine on long term use. It is therefore an object of the present invention to provide an alternative fuel source that does not contain significant amounts of fatty acid methyl esters. It is a further object of the present invention to provide an alternative fuel source that can run on existing engines without needing to retune the engines. It is still a further object of the present invention to provide a fuel additive that, when combined with diesel fuel, does not damage the engine on long term use. 

方法:Methods for preparing glyceryl ethers include reacting glycerol with an alkyl halide in the presence of a base, or with an olefin or an alcohol in the presence of an acid catalyst. The method is preferred because it uses relatively inexpensive reagents, water and an olefin, rather than the relatively more expensive alcohols. Suitable catalysts for use in the present invention include, but are not limited to, zeolites, clay montmorrilite, aluminum chloride, aluminum bromide, ferrous chloride and ferrous bromide. It is preferred that any alcohol used in the present invention contains less than five percent water, preferably less than approximately one percent water, to avoid saponification or hydrolysis of the triglycerides.

特徵:The fatty acid alkyl esters and the glyceryl ethers can be prepared by any means known to those of skill in the art. However, since methanol is less expensive than ethanol, blends of ethyl and methyl esters are slightly less expensive and can perform nearly as well in biodiesel fuel as pure ethyl esters, with the limitation of additional toxicity. To avoid engine corrosion, it is preferable to minimize the salt concentration in the fuel additive composition. In yet another embodiment, a neutral fuel additive is obtained without producing salts or using a washing step, by using a polymeric acid, such as Dowex 50.TM., which is a resin that contains sulfonic acid groups. These conditions provide lower molecular weight products, such as alkanes and aromatus, that have lower viscosities than the higher molecular weight fatty acid ester derivatives. 

 

US 5,308,365 

標題:Diesel fuel

應用:The present invention relates to a low sulfur diesel fuel which contains a dialkyl and a trialkyl derivative of glycerol in amount sufficient to reduce particulate matter emissions. The present invention relates to an improved diesel fuel which has reduced particulate matter emission characteristics and which contains an effective amount of a dialkyl ether and/or trialkyl ether derivative of glycerol and most preferably the glycerol di-t-butyl ether product mixture prepared by glycerol etherification with isobutylene or t-butanol. The present invention relates to the use of ether derivatives of glycerol which, when incorporated in standard 30-40% aromatic containing diesel fuel, provides reduced emissions of particulate matter, hydrocarbons, carbon monoxide and unregulated aldehyde emissions.  

方法:The diesel fuel formulations of the present invention consist essentially by volume of at least 85% diesel fuel hydrocarbons and 0.1 to up to 15% of the glycerol ether, preferably about 0.2 to 10% of the glycerol ether. Especially preferred diesel fuel formations of the invention comprise diesel fuel hydrocarbons and monoalkyl ether as above described together with peroxidic or nitrate cetane improvers such as ditertiary butyl peroxide, amyl nitrate, ethyl hexyl nitrate and the like. In addition to the use of the additives of the present invention in conventional carbon diesel fuels as above described, the additives also find utility with the newer generation of biodiesel fuels prepared from various vegetable type oils. % with conventional low sulfur diesel fuels in order to provide a resulting fuel with enhanced emission reduction characteristics. 

特徵:The diesel fuels of the invention have a low sulfur content, i.e. not more than 500 ppm by weight, preferably not more than 100 ppm and preferably not more than 60 ppm sulfur by weight. These additives have good solubilities in diesel fuel hydrocarbons, have superior water partition coefficient characteristics and are effective in reducing particulate matter emissions. The glycerol ether product is soluble in all portions with the methyl soyate, and indeed it has been found that a blend of the glycerol ether with methyl soyate has certain special and unique utilities. An additional feature of the above described mixtures of the methyl soyate with the glycerol ether mixture is that the resulting mixture possesses unique solvent characteristics. Not all oxygenates that are highly polar have good solubility in the new low aromatic reformulated diesel fuels. 

US 4,451,265

標題:Diesel fuel-aqueous alcohol microemulsions

應用:This invention relates to diesel fuel-alcohol blends and to a novel surfactant system for obviating the characteristic problems of prior art compositions.  

目標:In accordance with this discovery, it is an object of the invention to enable hybridizing diesel fuel with relatively high levels of aqueous alcohol. It is also an object of the invention to prepare diesel-alcohol fuels which exhibit high water tolerance. Another object of the invention is to enhance the combustion properties of diesel fuel by incorporation of microemulsified water droplets. Finally, it is an object and advantage of the invention to accomplish the aforementioned objectives by means of a simple and universally applicable surfactant system.

方法:Hybrid fuel microemulsions are prepared from diesel fuel, water, alcohol, and a novel surfactant system comprising N,N-dimethylethanolamine and a long-chain fatty acid substance. We have now developed a hybrid diesel fuel composition in which unexpectedly high levels of water and alcohol are held in a stable microemulsion at extremely low temperatures by means of a novel surfactant system prepared from two components. The novel surfactant system consists essentially of the reaction product of (1) N,N-dimethylethanolamine (DMEA) and (2) a long-chain fatty acid substance selected from the group of monocarboxylic acids having a chain length of C.sub.9 -C.sub.22 and mixtures thereof. The double surge tank included a boost fan to maintain atmospheric pressure at the inlet of the engine.

特徵:These fuels are characterized by high water tolerance and low-temperature stability, and are particularly adaptable to the utilization of aqueous ethanol as the alcohol source. Of course, the advantages of the invention are best realized by employing the alcohol in aqueous form. The minimum ASTM cetane value for No. 2 diesel oil is 40, though fuel formulations in accordance with this invention having cetane values as low as about 30 perform remarkably well in engine tests. Also, as the ratio of water:ethanol decreases, the tolerance of the system to phase separation increases, thereby either permitting the use of less surfactant, or allowing the ratio of ethanol to diesel oil to be increased. By proper selection of surfactant level, they can be readily formulated to have critical solution temperatures down to about -18.degree. C. 

US 6,398,707(台灣申請之專利)

標題:Method of preparing lower alkyl fatty acids esters and in particular biodiesel

應用:The present invention relates to a technique for enhancing the activity of an immobilized lipase, and a technique for regenerating a deactivated immobilized lipase, in which an alcohol with a carbon atom number not less than three is used to swell and/or clean said immobilized lipase. Said immobilized lipase is particularly useful in a method of preparing biodiesel by transesterification of triglycerides and a lower alcohol. The present invention relates to techniques for improving the activity of an immobilized lipase and for regenerating a deactivated immobilized lipase, wherein said immobilized lipase is particularly useful in a method of generating biodiesel by transesterification of triglycerides and a lower alcohol. Therefore, nearly all commercial strong base processes for producing biodiesel use pure vegetable oils as the raw material.   

目標:One objective of the present invention is to provide a method suitable for enhancing the activity of an immobilized lipase. Another objective of the present invention is to provide a method for regenerating an immobilized lipase having a reduced activity. Still another objective of the present invention is to provide a method of preparing a lower alkyl fatty acid ester, in particular biodiesel, by transesterification or esterification of a fatty acid glyceride or a free fatty acid with a lower alcohol using a pretreated or regenerated immobilized lipase as the catalyst. The present invention provides a method of preparing a C 1 -C 3 alkyl ester of a fatty acid by transesterification or esterification of a fatty acid glyceride or a free fatty acid with a C 1 -C 3 alcohol, characterized in that a pretreated immobilized lipase is used to catalyze the transesterification or esterification, wherein said pretreated immobilized lipase is prepared by immersing an immobilized lipase in an alcohol having a carbon atom number not less than 3 for a period of time, preferably from 0.5-48 hours, and more preferably from 0.5-1.5 hours.

方法:The inventors also observe that methanol is easier to be absorbed by the immobilized lipase than an oil. Preferably, said immobilized lipase is immobilized on a porous support. When n-hexane is used in the immersion pretreatment, the activity of the pretreated immobilized lipase is close to that of an immobilized lipase that receives no pretreatment. The deactivated lipases were subjected to the following washing operations to see whether the activity could be resumed. 

特徵:An alcohol having a higher number of carbon atoms is less poisonous to the immobilized lipase. The results indicate that the immersion pretreatment not only is not poisonous to the immobilized lipase, but also, under certain circumstances, increases the resistance of the immobilized lipase to the poisoning of methanol and ethanol. The immersion in a non-toxic alcohol has a better effect than the immersion in biodiesel, wherein the activity of the immobilized lipase pretreated by the former is 40% higher than the latter. When an immobilized lipase was pretreated according to the present invention, not only the initial activity of the pretreated immobilized lipase is increased significantly, but also the pretreated lipase has a higher resistance to the toxicity of methanol, as shown in the following example. The immersion of non-toxic alcohol indeed increases the resistance of the immobilized lipase to methanol, wherein iso-propanol and 2-butanol have a better effect.