TRƯỜNG ĐẠI HỌC BÀ RỊA – VŨNG TÀU

CÔNG NGHỆ TỔNG HỢP HỮU CƠ VÀ HÓA DẦU

(ORGANIC SYNTHEIS AND PETROCHEMICAL PROCESSES)

Giảng viên: TS. Tống Thị Minh Thu

Bộ môn: Công nghệ kỹ thuật Hóa học- Hóa dầu
1
 TỔ CHỨC DẠY VÀ HỌC
NỘI DUNG Lên lớp Ghi chú
Tổng số Lý thuyết Bài tập, thảo luận
Chương 4. Qúa trình tổng hợp trên cơ sở 6 3 3 Bài giảng + báo
Methane và các Paraffin khác cáo + thảo luận+
tự học
i. Hóa học trên cơ sở Methane
4.1. Tổng hợp Ammoniac
4.2. Tổng hợp Urea
4.3. Tổng hợp Methanol
a. Methyl t-butyl ether
b. Formaldehyde, Polyacetals (xem chương 9)
c. Acetic acid
4.4. Tổng hợp Fischer – Tropsch
4.5. Tổng hợp Dimethyl ether (DME), Dimethyl
carbonate

ii. Hóa học trên cơ sở các Paraffin khác (giới

thiệu) Tự học
4.6. Hóa học trên cơ sở Ethane, Propane, Butane
4.7. Oxy hóa Naphta nhẹ
4.8. Oxi hóa, Sulfo hóa Paraffin bậc cao
Ammonia synthesis
™ Uses of ammonia
Introduction
Uses
™ of Hydrogento ammonia synthesis • Mp: - 77 OC, bp:
Ammonia
Ammonia
™ production
Synthesis (P4)via : -33.34 °C
1. Partial Oxidation
Methanol Synthesis(POX)
(P5)
2. Steam Reforming
Formaldehyde Synthesis (P6) • Density:
Thermodynamics
Urea
™ Synthesis (P7) aspects 0.73 kg/m3 (1.013 bar
™ Kinetic aspects
at 15 °C);
™ Process conditions
Uses of Ammonia
1. Agricultural and fertilizer industry
– Production of ammonium phosphate, (NH4)3PO4
– Production of ammonium nitrate, NH4NO3
– Production of ammonium sulphate, (NH4)2SO4
– source of protein in livestock feeds for cattle, sheep and goats
2. Nitric Acid Production – used in making explosives such as TNT
3. Ammonia-soda industry – uses ammonia for producing soda ash
4. Petroleum industry uses ammonia to
– neutralize acid constituents of crude oil
– protect equipment from corrosion
5. Rubber industry – prevent premature coagulation by stabilizing natural rubber
6. Pulp and paper industry – for pulping wood
7. Textile industry – manufacture of synthetic fibers such as nylon and rayon.
8. Plastics industry – manufacture of phenolics and polyurethanes.
Introduction to Ammonia Synthesis
❖ Steps in NH3 synthesis
• Preparation of feedstock (synthetic gas)
• NH3 synthesis
• Product purification
❖ Stoichiometry of the reaction
• N2 + 3H2 2NH3
❖ Ammonia can be produced through a series of operations employing :
• 1. Partial oxidation (POX)
• 2. Gasification of heavy hydrocarbon fractions or coal
• 3. Steam reforming of methane or naphtha
• React with MDEA: R3N + H2O + CO2 ↔ R3NH+ + HCO3- Hexahydropyrazine;
Piperazidine;
• React with piperazine: 2R2NH + CO2 ↔ R2NH2+ + R2N-COO- Diethylenediamine
❖ Preparation of feedstock
1. From partial oxidation of methane / naphtha
a. Air distillation
b. Partial oxidation of “HC” with oxygen
c. Removal of C and recovery of heat
d. Removal of H2S and conversion to S
e. Catalytic conversion of CO by steam (shift conversion)
CO + H2O CO2 + H2
f. CO2 removal
g. CO removal by liquid N2
2. From steam reforming
a. Steam treatment (primary reforming)
b. Conversion of residual methane by air
c. Catalytic conversion of CO by steam
CO + H2O CO2 + H2
d. CO2 removal
e. CO removal
Công nghệ reforming
Thermodynamics Aspects

The thermodynamic considerations imply that :

1. Once-through conversion of feed gas is limited, recycling results in synthesis loop operating at high P
2. Partial conversion of reactants at high pressure invites large mechanical energy costs
3. Use of low temperatures reduces reaction rate
 Kinetic Aspects
❖To accelerate the approach to equilibrium, employ catalyst
Oxide catalysts from group 7 metals
e.g. Fe (Fe3O4), promoters Al2O3, K2O, SiO2, MgO, CaO
❖To improve catalyst stability, activity and resistance to poisoning
Ru, modified Rb, Ti, Ce compounds
❖Yield (max) @ equilibrium : High P & Low T (according to thermodynamics)
❖Operating condition
P : 150 – 350 atm
T : 400 – 550oC (according to kinetics)
- to achieve acceptable conversion
 Process Conditions
❖Process for ammonia synthesis started of with high pressure operation
( 30 to 35 × 106 Pa abs)
❖Low pressure process is subsequently adopted 20 to 25 × 106 Pa abs
❖Subsequently, operation can be carried out at 15 to 20 × 106 Pa abs
with very pure feed including liquid nitrogen scrubbing
❖ICI, SNAM Progetti (Societa Nazionale Metanodotti) and Pullman-Kellogg recommends
operation at 5 × 106 Pa abs
• enhance energy optimization but
• requires larger catalyst loading and higher unconverted gas recirculation rates
Temperature range of operation : 480 to 550 oC
Ammonia synthesis loop
Sx khí tổng hợp bằng pp oxi hóa không hoàn toàn (qt khí hóa)- Partial oxidation
Nguyên liệu:
• Khí tự nhiên, HC nặng (phân đoạn FO), Than đá…
Các phản ứng
• Phản ứng cháy ở nhiệt độ cao (CO là sản phẩm chính) •
• Phản ứng CO với hơi nước (hơi nước được tạo ra •
trong phản ứng hoặc đưa vào)
•
• Phản ứng phân hủy cacbon
• Các phản ứng khác
•
Phản ứng tổng quát

• Đối với nguyên liệu là khí tự nhiên

• Đối với nguyên liệu: HC nặng

Latest improvements in ammonia production by steam reforming
Company Feedstock Process description
Ammonia Casale SA Natural gas (NG) Process produces anhydrous ammonia from natural gas by applying Casale's high-efficiency
secondary reformer design, axial-radial technology for shift conversion, ejector ammonia wash
system, axial-radical technology for ammonia converter and advanced waste-heat boiler design in the
synthesis loop.
Haldor Topsøe A/S Natural gas, naphtha, Low-energy ammonia technology produces ammonia from a variety of hydrocarbon feed-stocks
fuel oil ranging from natural gas to heavy naphtha

Linde AG Light hydrocarbons LCA process simplifies conversion of light hydrocarbons to ammonia. It consists of a modern
hydrogen plant, standard nitrogen unit and high-efficiency ammonia synthesis loop

Udhe GmbH Natural gas, LPG, Process uses conventional steam reforming synthesis gas generation (front-end) and an ammonia
naphtha synthesis loop
Kellogg Brown & Root, Hydrocarbons To produce ammonia from hydrocarbon feedstocks using a high-pressure heat exchange-
Inc. based steam reforming process integrated with a low-pressure advanced ammonia synthesis
Process

Kellogg Brown & Root, Hydrocarbons To produce ammonia from hydrocarbon feedstocks and air. Process features include a mild
Inc. primary reforming, secondary reforming with excess air, cryogenic purification of syngas, and
synthesis of ammonia over magnetite catalyst in a horizontal converter

Kellogg Brown & Root, Hydrocarbons To produce ammonia from hydrocarbon feedstocks using a high-pressure heat exchange-
Inc. based steam reforming process integrated with cryogenic purification of syngas
Licensor: Ammonia Casale SA, Switzerland - CONTACT
Licensor: HaldorA Topsøe A/S - CONTACT
Licensor: Linde AG - CONTACT
Licensor: Uhde GmbH - CONTACT
Licensor: Kellogg Brown & Root, LLC - CONTACT
Licensor: Kellogg Brown & Root, LLC - CONTACT
Licensor: Kellogg Brown & Root, LLC - CONTACT
 METHANOL PRODUCTION
❖ Uses of methanol
❖ Introduction to methanol synsthesis
❖ Methanol production via :
• 1. Partial Oxidation (POX)
• 2. Steam Reforming
❖ Thermodynamics aspects
❖ Kinetic aspects
❖ Process
Latest improvements in Methanol production by steam reforming
Company Feedstock Process description
Davy Process Natural gas or associated The process produces methanol from natural gas or associated gas via a reforming step or
Technology, gas from syngas generated by gasification of coal, coke or biomass. The reforming/gasification
UK/Johnson Matthey step is followed by compression, methanol synthesis and distillation
Catalysts
Methanol Casale SA Natural gas To produce methanol from natural gas. The process is based on Casale's highly efficient
plate-cooled technology for the methanol converter

Methanol Casale SA Natural gas To produce methanol from natural gas. The process is based on Casale's highly efficient
axial-radial pre-reformer, high-efficiency auto-thermal reformer design and plate-cooled
technology for the methanol converter

Toyo Engineering Corp. Natural gas-based Federal-grade AA refined methanol is produced from natural gas-based synthesis gas and
(TOYO) synthesis gas and naphtha using Synthesis Gas Generation technologies and proprietary MRF-Z reactor.
naphtha
Lurgi GmbH Natural gas, naphtha, Oxygen-operated syngas generation, two-step isothermal synthesis with maximum yield and
vacuum residue, natural very large single-train capacity
gas

Uhde GmbH Natural gas, LPG and Process uses steam-reforming synthesis gas generation and a low-pressure methanol
heavy naphtha synthesis loop technology

Haldor Topsøe A/S Natural gas, naphtha, Process produces methanol from natural or associated gas feedstocks using two-step
fuel oil reforming followed by low-pressure synthesis.
Licensor: Methanol Casale SA, Switzerland - CONTACT
Licensor: Lurgi GmbH, a member of the Air Liquide Group - CONTACT
Licensor: Toyo Engineering Corp. (TOYO) - CONTACT
Licensor: Uhde GmbH is a licensee of Johnson Matthey Catalysts’ Low-Pressure Methanol (LPM) Process - CONTACT
Licensor: Haldor Topsøe A/S - CONTACT
FORMALDEHYTE PROCESS
Licensor: Uhde Inventa-Fischer - CONTACT
DME SYNTHEIS PROCESS
Cơ chế của xúc tác
Kết quả khảo sát TPR và XPS cũng chỉ ra ở hàm lượng CuO thấp (<30% khối lượng)
các ion Cu2+ trong mạng tinh thể ZnO sau khi bị khử sẽ hình thành các lớp Cu0 và Cu1+
hòa tan trong mạng tinh thể của ZnO. Với xúc tác có hàm lượng CuO từ 30 – 50%, Cu 2+
dạng tự do sẽ chiếm ưu thế cao trong oxit ZnO và CuO. Ở hàm lượng CuO cao hơn, tinh
thể CuO sẽ dư thừa và nồng độ của Cu1+ dạng bền vững sẽ rất thấp. Vì vậy, xúc tác trong
quá trình này sử dụng có thành phần là: 30-36% Cu/ 20-14% Zn/ 50% Al và chất mang
đưa vào có thành phần với xúc tác là: 50% wt CuO-ZnO-Al2O3 với 50% wt γ-Al2O3 sẽ cho
hiệu suất DME cao (>44%).
 FISCHER-TROPSCH

The three basic process steps

1. Synthesis gas preparation
2. FT synthesis
3. Product upgrading
FISCHER-TROPSCH
Reaction pathways in the Fischer-Tropsch synthesis
1. generation of the chain initiator
2. chain growth or propagation
3. chain growth termination or desorption

'CO-insertion' mechanism for chain growth in the

Fischer-Tropsch synthesis