JPS60122701A - Production of hydrogen by partial oxidation of heavy hydrocarbon in cdq equipment - Google Patents

Abstract

PURPOSE:To produce hydrogen at a low cost by the efficient partial oxidation of heavy hydrocarbon while saving energy and eliminating carbon trouble by utilizing a coke dry-quenching equipment used in the manufacture of coke as a gas producer. CONSTITUTION:The temp. of the prechamber 2 of a gas producer 1 is kept at about 920-980 deg.C. Heavy hydrocarbon such as petroleum asphalt is preheated with a preheater 4 and introduced into the prechamber 2. At the same time, O2 is blown into the prechamber 2 by a larger volume than the volume of O2 required by a reaction represented by equation I , and the reaction temp. is kept at about 1,000-1,100 deg.C. An excess of O2 prevents a drop in temp. due to the endothermic reaction represented by the equation I by an exothermic reaction represented by equation II. In the cooling chamber 3, endothermic reactions represented by equations III, IV are caused by blowing steam to accelerate the cooling of lump coke. Gas produced by the partial oxidation of the heavy hydrocarbon is fed to a boiler 6 through a dust collector 5 to recover the sensible heat. The gas is desulfurized in a desulfurizer 9 and introduced into a pressure swing adsorber 10, where H2 is separated.

Description

DETAILED DESCRIPTION OF THE INVENTION [Technical Field] The present invention relates to a method for producing hydrogen at low cost by partially oxidizing heavy hydrocarbons by effectively utilizing coke dry fire extinguishing equipment (CDQ) as a gas generating furnace.

[Prior art]

By partially oxidizing conventional heavy hydrocarbons (CO+
H11) The Texaco method and the TBG method are generally well known as methods for obtaining multi-INK gases.

The Texaco method is (heavy hydrocarbon) +10z →mco + nFh +
rH2S (It (heavy hydrocarbon) + pot → qcOx
+ tH20-f21 By combining the exothermic reaction of formula (2) and the endothermic reaction of formula (1), 1200-1500
It is characterized in that it is carried out at a high temperature of 86°C and a high pressure of 9/1-dG. However, the disadvantage is that about 2% of the raw material becomes soot.

On the other hand, the catalytic partial oxidation represented by the TBG method is
It is carried out at a temperature of 16 to 950°C in a row i'1 of about 16 kQ/crl G. In this case, what is important is that the catalyst is required to suppress the soot generation by minimizing the sulfur poison % CH4 formation.

Since these methods require equation (2) and inevitably use a large amount of 02, the TBG method employs an externally heated fixed bed method.

Catalysts are also expensive, and their lifespan is said to be about two years.

Conventional methods have not yet succeeded in producing a catalyst that does not generate soot, and it is said that the generation of several tons of soot is unavoidable.

The disadvantage of the partial oxidation method is that it requires a high cost for reaction equipment for equation (2). Therefore, in the conventional method, K
However, it is expensive to steam reform naphtha! The manufacturing method is also less economical.

When comparing the TBG method and the TEXACO method, the TBG method is said to be slightly cheaper.

The reason for the reaction at high pressure is to reduce the 02 basic unit, which is 1.10, 85 (kg
It is said that this is caused by a decline in /, ).

[Purpose of the invention]

The purpose of the present invention is to save energy and eliminate carbon troubles in the process of adding high value to heavy hydrocarbons, and to develop an economical hydrogen production method by partial oxidation of heavy hydrocarbons.

[Summary of the invention]

In view of the above-mentioned conventional technology and purpose, the present inventors focused on the CDQ equipment used in coke manufacturing plants, and by utilizing it as a gas generating furnace, they were able to efficiently partially oxidize heavy hydrocarbons. This invention was invented based on the knowledge that hydrogen could be produced by partially oxidizing heavy hydrocarbons. Injecting the generated gas, on the other hand, the coke is cooled by an endothermic reaction by blowing steam into a part of the cooling chamber of the coke extinguishing equipment, and by blowing circulating gas after sensible heat recovery from the lower part of the cooling chamber. It is characterized by a hydrogen production method by partial oxidation of heavy hydrocarbons using CDQ equipment.

FIG. 1 is a process diagram of the method of the present invention, and the present invention will be described in more detail based on FIG.

In order to suppress the reaction of the above-mentioned formula (2) as much as possible, the present invention
This is an attempt to use the sensible heat of red-hot coke discharged from a coke oven (not shown) for producing metallurgical coke as a substitute for the reaction heat in equation (2). The coke waste heat recovery equipment (gas generation furnace) 1 is a partially modified conventional CDQ equipment. The temperature of this brake chamber portion 2 is maintained at 920 to 980°C. On the other hand, petroleum-based heavy oil, such as heavy hydrocarbons such as asphalt, is preheated in the preheater 4, and at the same time, the amount of 02
2 into the Brechamber part 2 and the reaction temperature was set to 10,000.
The temperature was maintained at ~1100°C. The surplus 02 was generated by the exothermic reaction of the following equation (3) (preventing the temperature drop due to the endothermic reaction of the equation 11).

(Coke) + 1/20x → Co -131 On the other hand, steam is blown into the 6th part of the ring champer (coke) 10 L O-+ Co 10 Mountains - (4) (
Coke) + 2)hO-+ COz 1,0002Hz -
f51f4) F (Produced the endothermic reaction of formula 51 and promoted cooling of the coke lump.

A part of the exhaust gas from the boiler 6 is circulated through the circulation waste line 7 to the cooling chamber part 6 in order to reduce the temperature of the discharged coke to 250° C. or lower.

The dust produced by the partial oxidation of heavy hydrocarbons is removed by a dust collector 5, and then sensible heat is recovered by a boiler 6. After that, after desulfurizing with gas t and de-sulfurizer b9, PSA
(Pressure swing adsorption device i) introduced at 10 Hz,
is separated, but with a shift comparator 8 in between, C
It is also possible to convert O into H2 and then introduce it into the PSA 10.

In this way, heavy hydrocarbons are introduced into ecDQ, and the function of CDQ is effectively utilized, and the amount of SI02 used is reduced by utilizing sensible heat of coke in the reaction of formula 1), and high value-added hydrogen is produced. It is.

Next, a detailed explanation will be given below based on examples.

〔Example〕

Example 1 Red-hot coke discharged from a coke oven was converted into a gas generating furnace at T' 50/H and supplied to 90DQ equipment 1. Petroleum-based heavy oil shown in Table 1 was preheated to 180°C and heated to 280°C.
/hr and at the same time oxygen was injected into prechamber 2.
It was injected at a rate of 5,680”/hr.

The amount of steam blown into the lower part 6 of the furnace is 1400 kg//hr
The circulating gas amount was 30,000"/hr, and the generated gas composition was CH4'0.8 at the gas generator outlet.
Volume CH CO12,2#% H365,0% CO□ 6.7 CHHz S 0.3 CHN2 0.5 CH Softening point 5a5℃ Conradson Carbon 20.8% CB 5.1 Weight% H10,4# N O,7g S3.2.

Q O, 5# Ash content 0.1# The discharged coke can be used as coke for the furnace.

Furthermore, this generated gas was introduced from the purified COG to the PSA device 10 for the purpose of separating H2, and H2 could be separated.

Embodiment 2 Gas generated from a coke oven is simmered with ammonium water and then led to a tar decanter. Even at this point, this gas still contains a considerable amount of heavy hydrocarbons as shown below. COI 6.9% by weight (dry gas space)"'Hm
IaOtOx 1,2.

City 10.8.

Co　17.6　z C) I4 41.1° C2H @ (1B.

Ni 3.6.

Crude COG was blown into the CDQ equipment 1 with the main purpose of partially oxidizing this 18 heavy f#-〇 heavy hydrocarbon. 47/f(r
At a red hot coke feed rate of 42,300 N”/
At the same time, 0 □ was blown in at 8.30 ONR/hr, and the next gas n [
achieved success. Of course, I had to inject steam into the CDQT section 3. A circulating gas cycle was also implemented.

CO26,1'B volume % (dry ht base) Hz 69.7
-CH CO18, 1t% CI (a 5.4
After converting to O course H2, it can also be led to PSAI O.

High value-added hydrogen and surgical gas can be used as a gas generating furnace by modifying the CDQ equipment. Cheap 111 hydrogen that can use soot and its coke lumps as a collector! It is a construction method.

[Brief explanation of drawings]

FIG. 1 is a process diagram of the unexploded IJIJ method. 1: CDQ 2: Breech chamber part 6: Part of cooling chamber 6: Boiler 7: Circulating gas 5y 9
:Undressed UR10: PSA0 agent 9P Rito Kimura Saburo

Claims (1)

[Claims] (1) In a method of partially oxidizing heavy hydrocarbons to produce hydrogen, heavy hydrocarbons and oxygen are blown into a part of the prechamber of a coke dry fire extinguishing equipment, the generated gas is taken from the OL, and then the exhaust heat from the boiler, etc. The recovery equipment recovers the sensible heat of the produced gas, and if necessary, the gas after heat recovery is introduced into the PSA via a desulfurization pupil to produce hydrogen from the gas, while the coke is cooled by the coke extinguishing equipment. Hydrogen is generated by partial oxidation of heavy hydrocarbons using CDQ equipment, which is characterized by an endothermic reaction by blowing steam into a part of the cooling chamber, and cooling by blowing circulating gas from the bottom of the cooling chamber after recovering sensible heat. Manufacturing method. (21) The method for producing hydrogen by partial oxidation of heavy hydrocarbons according to claim ii, characterized in that the boiler exhaust gas is introduced into a shift converter to produce hydrogen.