公开(公告)号：WO2017078582A1

公开(公告)日：2017-05-11

申请号：PCT/SE2015/051164

申请日：2015-11-04

Applicant: SCA FOREST PRODUCTS AB

Inventor： KUGGE, Christian ,  HULTGREN, Anders ,  DANNENBAUER, Kai ,  LIEBOLD, Claudia ,  HUBER, Florian

IPC: C10L1/02 ,  C07G1/00 ,  C08H7/00 ,  C10G1/00 ,  C12P7/64 ,  D21C11/00

CPC classification number: C07G1/00 ,  C08H6/00 ,  C10G1/086 ,  C10G3/46 ,  C10G3/47 ,  C10G3/48 ,  C10G3/49 ,  C10G3/50 ,  C10G2300/1011 ,  C10L1/04 ,  C12P7/64 ,  Y02P30/20

Abstract: A process for producing a hydrocarbon product from a lignin oil, said lignin oil having an oxygen content of 10-30 wt-%, an average weight molecular weight of 500-800 g/mol with a polydispersity of 2, a heating value of 25-35 MJ/kg, a water content of 0-1.5 wt-%, a sodium content of 400-500 ppm, a potassium content of 50-100 ppm, a sulfur content of 1-2.5 wt-% and a total acid number of 110-125 mg KOH/g oil, wherein the process for producing the hydrocarbon product comprises the steps of treating the lignin oil in a rector in the presence of one or more of a hydrodesulfurization catalyst selected from NiMo on alumina or CoMo on alumina; or a hydrodesulfurization and cracking catalyst selected from NiMo on zeolite or CoMo on zeolite, or a hydrodeoxygenation and cracking catalyst selected from NiO on zeolite, zeolite alone or combinations thereof, or a hydrodeoxygenation catalyst selected from Ni/NiO, Cu/Cr, Pd/Cu, or Pt on a support material, such as chromite and/or alumina and/or zirconia and/or graphite and/or carbon and/or silica; or combinations thereof, and applying a H 2 pressure of 30-160 bar, preferably 50-150 bar, a gas to oil ratio (GTO) of 200- 2000 l/l, preferably 500-1500 l/l, at a temperature of 290-400 °C, preferably 300-360 °C, and with a liquid hourly space velocity (LHSV) of 0.25-2 h -1 and preferably 0.5-1 h -1 followed by cooling the reaction product from the reactor to 20-30 °C, and separating the reaction product by phase separation, into a gaseous phase, a liquid hydrocarbon product phase, and a water phase, thereby obtaining the hydrocarbon product, and a hydrocarbon product.

Abstract translation: 一种由木质素油生产烃产物的方法，所述木质素油具有10-30重量％的氧含量，500-800g / mol的平均重量分子量和多分散性 为2，热值为25-35MJ / kg，含水量为0-1.5重量％，钠含量为400-500ppm，钾含量为50-100ppm，硫含量为1-2.5 重量％和总酸值为110-125mg KOH / g油，其中生产烃产物的方法包括以下步骤：在一种或多种选自以下的加氢脱硫催化剂存在下在反应器中处理木质素油： 氧化铝上的NiMo或氧化铝上的CoMo; 或选自沸石上的NiMo或沸石上的CoMo或选自沸石上的NiO，单独沸石或它们的组合的加氢脱氧和裂化催化剂或选自Ni / NiO，Cu / Cr，Pd / C的加氢脱氧催化剂的加氢脱硫和裂化催化剂， Cu或Pt在载体材料上，例如铬铁矿和/或氧化铝和/或氧化锆和/或石墨和/或碳和/或二氧化硅; 或其组合，并且施加30-160巴，优选50-150巴的H 2 / N 2压力，200-2000l / l，优选500-1500l的气体与油的比率（GTO） / l，温度为290-400℃，优选300-360℃，液时空速（LHSV）为0.25-2h -1，优选0.5-2.5℃， 然后将反应产物从反应器冷却到20-30℃，并通过相分离将反应产物分离成气相，液态烃产物相和 从而获得烃产物和烃产物。

公开(公告)号：WO2017048164A1

公开(公告)日：2017-03-23

申请号：PCT/SE2015/050970

申请日：2015-09-16

Applicant: SCA FOREST PRODUCTS AB

Inventor： KUGGE, Christian ,  HULTGREN, Anders ,  FRÖJDHOLM, Hampus

IPC: C10L1/02 ,  C07G1/00 ,  C08H7/00 ,  C12P7/64 ,  D21C11/00

CPC classification number: C07G1/00 ,  C08H6/00 ,  C08H8/00 ,  C10L1/02 ,  D21C11/0007

Abstract: A process for batch wise production of bio-oil comprising the steps of a) preparing a black liquor composition comprising kraft black liquor, and having a hydroxide ion concentration of -40 g/l, preferably 5-15 g/l based on the volume of black liquor, if necessary adjusting the hydroxide ion concentration by means of addition of an acidifying agent (AA1);b) reacting the black liquor composition in a reactor (R) and reacting the black liquor composition at 220-350 °C for 10-120 minutes, preferably 30-60 minutes in the absence of a solid catalyst; or at 180- 240 °C for 10-120 minutes, preferably 30-60 minutes, in the presence of a solid catalyst, thereby causing depolymerization of lignin in the black liquor;c) cooling the composition to a temperature below the boiling point of a solvent to be added in a subsequent step;d) acidifying the composition by adding one or more acidifying agents (AA2) until a pH of 4-5 is reached;e) adding a solvent (S) to the composition, in order to extract oil from the composition;f) separating the composition by phase separation in a first separation step (S1) intoan oil phase (A) comprising solvent, oil, and organic acids; a first water phase (B) comprising water, salts, and non-depolymerized lignin solids; a second water phase (C1) comprising water and salts;g) filtering (F2) the first phase (A) to remove any particles;h) desalting the filtered oil phase (A) byi) washing it by adding water and separating by phase separation in a second separation step (S2) into an oil phase (D) comprising oil and solvent, and a third water phase (C2) comprising salts; orii) adding adsorbent and/or absorbent material or ion exchange material, or combinations thereof;i) evaporating (E2) the solvent comprised in the oil phase (D), thus obtaining a bio-oil.

Abstract translation: 一种分批生产生物油的方法，包括以下步骤：a）制备包含牛皮纸黑液的黑液组合物，其氢氧根离子浓度为-40g / l，优选为5-15g / l，基于体积 黑色液体，如果需要，通过加入酸化剂（AA1）调节氢氧根离子浓度; b）使黑液组合物在反应器（R）中反应并使黑液组合物在220-350℃下反应10 -120分钟，优选30-60分钟; 或在180-240℃下在固体催化剂存在下进行10-120分钟，优选30-60分钟，从而引起木质素在黑液中的解聚; c）将组合物冷却到低于 在随后的步骤中加入的溶剂; d）通过加入一种或多种酸化剂（AA2）酸化组合物直到pH达到4-5; e）向组合物中加入溶剂（S），以便 从组合物中提取油; f）通过在第一分离步骤（S1）中的相分离成包含溶剂，油和有机酸的油相（A）分离组合物; 包含水，盐和未解聚的木质素固体的第一水相（B）; 包含水和盐的第二水相（C1）; g）过滤（F2）第一相（A）以除去任何颗粒; h）将过滤的油相（A）脱盐，然后通过加入水洗涤并通过相分离 在第二分离步骤（S2）中分离成包含油和溶剂的油相（D）和包含盐的第三水相（C2）; orii）加入吸附剂和/或吸收材料或离子交换材料或其组合; i）蒸发（E2）包含在油相（D）中的溶剂，从而获得生物油。

公开(公告)号：WO2017048163A1

公开(公告)日：2017-03-23

申请号：PCT/SE2015/050969

申请日：2015-09-16

Applicant: SCA FOREST PRODUCTS AB

Inventor： KUGGE, Christian ,  HULTGREN, Anders ,  FRÖJDHOLM, Hampus

IPC: C10L1/02 ,  C07G1/00 ,  C08H7/00 ,  C12P7/64 ,  D21C11/00

CPC classification number: C07G1/00 ,  C08H6/00 ,  C08H8/00 ,  C10L1/02 ,  D21C11/0007

Abstract: A process for continuously producing bio-oil comprising the steps of a) forming a black liquor composition in a mixing tank (T) by mixing kraft black liquor,acidifying agent (AA1), in an amount sufficient to adjust the hydroxide ion concentration of the black liquor to 1-40 g/l, preferably 5-15 g/l based on the volume of black liquor;b) introducing the black liquor composition into a reactor (R), applying a pressure of 5-150 bar of H 2 or H 2 /CO, and a hydrogen/ black liquor composition flow ratio of 50-3000 l/l, preferably 100-600 l/l, and reacting the black liquor composition at 220-350 °C for 10-120 minutes, preferably 30-60 minutes in the absence of a solid catalyst; or at 180-240 °C for 10-120 minutes, preferably 30- 60 minutes, in the presence of a solid catalyst,thereby causing depolymerization of lignin in the black liquor composition;c) cooling the composition to a temperature below the boiling point of a solvent to be added in a subsequent step;d) acidifying the composition by adding one or more acidifying agents (AA2) until a pH of 4-5 is reached;e) adding a solvent (S) to the composition, in order to extract oil from the composition; f) separating the composition by phase separation in a first separation step (S1) into an oil phase (A) comprising solvent, oil, and organic acids; a first water phase (B) comprising water, salts and non-depolymerized lignin solids; a second water phase (C1) comprising water and salts;g) filtering (F2) the first phase (A) to remove any particles;h) desalting the filtered first phase (A) by i) washing it by adding water and separating by phase separation in a second separation step (S2) into an oil phase (D) comprising oil and solvent, and a third water phase (C2) comprising salts; or ii) adding adsorbent and/or absorbent material or ion exchange material, or combinations thereof;h) evaporating (E2) the solvent comprised in the oil phase (D), thus obtaining a bio-oil;and j) recycling solvent evaporated in step i) to step e).

Abstract translation: 一种用于连续生产生物油的方法，包括以下步骤：a）通过将牛皮草黑液，酸化剂（AA1）以足以调节氢氧化物离子浓度的量来混合，在混合罐（T）中形成黑液组合物 黑液为1-40g / l，优选为5-15g / l，基于黑液的体积; b）将黑液组合物引入反应器（R）中，施加5-150巴的H 2压力或 H2 / CO，氢/黑液组成流量比为50-3000升/升，优选为100-600升/升，并将黑液组合物在220-350℃下反应10-120分钟，优选30- 在不存在固体催化剂的情况下60分钟; 或在固体催化剂存在下，在180-240℃下进行10-120分钟，优选30-60分钟，从而引起黑液组合物中木质素的解聚; c）将组合物冷却至低于沸点 的待添加的溶剂; d）通过加入一种或多种酸化剂（AA2）酸化所述组合物直到pH达到4-5; e）向所述组合物中依次加入溶剂（S） 从组合物中提取油; f）通过第一分离步骤（S1）中的相分离将组合物分离成包含溶剂，油和有机酸的油相（A）; 包含水，盐和未解聚的木质素固体的第一水相（B）; 包含水和盐的第二水相（C1）; g）过滤（F2）第一相（A）以除去任何颗粒; h）通过加入水来分离过滤的第一相（A），除去 在第二分离步骤（S2）中将相分离成包含油和溶剂的油相（D）和包含盐的第三水相（C2）; 或ii）添加吸附剂和/或吸收材料或离子交换材料或其组合; h）蒸发（E2）包含在油相（D）中的溶剂，从而获得生物油;和j）将溶剂蒸发掉 步骤i）到步骤e）。